JP2006276308A - Electrostatic charge image developing toner, method for manufacturing the same, developer for electrostatic charge image development, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having excellent grain size distribution characteristics and charge characteristics, and a method for manufacturing the same, and a developer for electrostatic charge image development using the electrostatic charge image developing toner, and an image forming method. <P>SOLUTION: The electrostatic charge image developing toner includes resin particulates containing a crystalline polymer and an amorphous polymer. The amorphous polymer and the crystalline polymer satisfy the relationship of the following formula (1): (Formula 1): δa-δc≥1.05[(cal/m1)<SP>1/2</SP>/25°C], where, δa: the solubility parameter of the amorphous polymer, δc; the solubility parameter of the crystalline polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner used for developing an electrostatic image in an electrophotographic apparatus utilizing an electrophotographic process such as a copying machine, a printer, a facsimile, and the like, a manufacturing method thereof, and the electrostatic image. The present invention relates to an electrostatic charge image developer using a developing toner and an image forming method.

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

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

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

On the other hand, along with the increasing demand for energy saving in recent years for image formation,
In the electrophotographic process, so-called low-temperature fixing toner is being actively developed to save power in the fixing process, which is one of the most energy consuming processes.

  In this case, lowering the fixing temperature of the toner usually lowers the glass transition point of the toner at the same time, so that the storage stability of the toner and the storage stability (offset) of the finally obtained output image are reduced. It becomes difficult to achieve both. In order to solve this problem, in order to achieve both low-temperature fixing and toner storage stability, the viscosity of the toner rapidly decreases near the fixing temperature while the glass transition point of the toner is kept high. It is necessary to have sharp melt properties.

  As a promising approach to the technical problem, a method using a crystalline resin having a sharp melt property as a binder resin has been proposed.

  However, it is difficult to obtain fine particles for using the crystalline resin as toner particles. To obtain this, the kneading and pulverization method is difficult to grind and the yield is low. There was a problem of lack (see, for example, Patent Documents 1 and 2). That is, in improving both the low-temperature fixability and the offset resistance, it is difficult to use a crystalline resin that is effective for the low-temperature fixability and the offset resistance in the melt-kneading pulverization method. Further, since the pulverization is performed, it is difficult to control the shape of the toner particles. In particular, it is difficult to reduce the particle size of the toner particles and to narrow the particle size distribution for the purpose of making the toner particles spherical and improving the image quality.

  As a means for solving the above problem, a technique of using a crystalline resin and an amorphous resin in combination instead of using a crystalline resin alone as a binder resin has been reported. This is because the presence of the amorphous resin portion facilitates pulverization. For example, a method using a crystalline resin and an amorphous resin in combination (see Patent Document 3), a method using a resin in which a crystalline resin and an amorphous resin are chemically bonded (see Patent Document 4), and the like. Can be mentioned. However, in these methods, the ratio of the amorphous resin is large, and the melting of the whole toner is governed by the softening temperature of the amorphous resin, so that the effect of low-temperature fixability is low.

  In addition, a wet manufacturing method in which toner particles are prepared by a chemical manufacturing method such as a dissolution suspension method has been studied (see Patent Document 5). When a wet manufacturing method such as a dissolution suspension method is used, toner particles that are difficult to knead and pulverize can be easily produced by dissolving them in an organic solvent and suspending and dispersing them in an aqueous medium. It is possible to easily produce spherical toner particles. In addition, the particle size distribution of the toner particles can be controlled. However, the solution suspension method using a crystalline resin has a problem in terms of environment that it is difficult to uniformly disperse a small amount of a component such as a colorant uniformly in a toner and that an organic solvent is used. In addition, the volume resistance value of the crystalline resin is lower than that of the conventionally used amorphous resin in the molecular weight region, and it is difficult to secure the charging characteristics necessary for electrophotography with the crystalline resin alone. is there.

Therefore, for the purpose of improving this problem, the emulsion or suspension resin fine particles containing these components are aggregated in a solution in which a crystalline resin is dissolved in a radical polymerizable monomer that forms an amorphous polymer. A so-called emulsion polymerization aggregation method for obtaining toner particles by fusing has been proposed (see, for example, Patent Documents 6 and 7).
However, these methods are not sufficient for obtaining the characteristics of the crystalline resin because the ratio of the crystalline resin contained in the toner is small. In these methods, the low-temperature fixability and image storability due to the sharp melt properties inherent to crystalline resins cannot be effectively extracted, so that sufficient low-temperature fixability can be achieved. I can't. Further, in the above cases, it is important to form a microdomain structure (sea island structure) in the final toner as described in the details of the invention in Patent Documents 6 and 7, and the crystalline substance is used as the domain. Although it has been shown that (island part) is dispersed in the sea part of the amorphous polymer of the main component, it is naturally not possible to use a crystalline substance as the main component in order to form this domain structure.

In addition, in the toner preparation method in which toner particles are prepared by carrying out an emulsion polymerization aggregation method in an aqueous medium using a crystalline resin, it is extremely difficult to control the particle diameter, particle size distribution, and toner charging characteristics. It becomes a big problem to use as. This is because it is difficult for the crystalline resin to impart sufficient chemical stability and mechanical stability necessary for the fine resin particles used in the emulsion polymerization aggregation method in an aqueous medium. It is necessary to introduce a polar group capable of ion dissociation into the resin. However, this polar group usually lowers the crystallinity of the resin and causes a problem in sharp melt low-temperature fixing, which is an object of the present technology.
Further, in this case, in order to give the amorphous polymer its role and to give a polar group to the particle surface, for example, a monomer containing a polar group is added to the amorphous polymer by a miniemulsion method as described in Reference 6. Although attempts have been made to copolymerize molecules, it is extremely difficult to copolymerize a simple polar group monomer in an aqueous medium in the miniemulsion method from the viewpoint of the polymerization mechanism. It is extremely difficult to obtain sufficient toner particle size and distribution control in the polymerization aggregation method.
Further, the problem of poor chargeability as a toner due to the low volume resistance value of the crystalline resin is the same in the toner by the emulsion polymerization aggregation method, and it is difficult to secure the charging characteristics necessary for the electrophotographic method.

  As described above, in the toner using the crystalline resin by the above-described method, the low-temperature fixing property which is an advantage of the crystalline resin, as well as sufficient charging property and offset resistance are ensured, and the charging property and particle size distribution sufficient as the toner are ensured. It is extremely difficult to impart characteristics and the like, and no toner that satisfies these toner characteristics has yet been provided.

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Laid-Open No. 2-79860 JP-A-1-163756 Japanese Patent Laid-Open No. 9-15902 JP 2001-42564 A JP 2001-42568 A

  The present invention relates to various problems related to the low-temperature fixing technology using the crystalline resin, an electrostatic image developing toner having excellent particle size distribution characteristics and charging characteristics, a production method thereof, and the electrostatic image development. An object of the present invention is to provide a developer for developing an electrostatic image using a toner and an image forming method.

In such a situation, the present inventors have conducted intensive research, and as a result, the following electrostatic charge developing toner and the production method thereof, the electrostatic charge image developer using the toner, and the image forming method were excellent. The present invention has been completed by finding out that the low-temperature fixing characteristics and the important charging characteristics as toner, the particle size distribution characteristics, and the document storage characteristics are compatible.
That is, the present invention
<1> An electrostatic charge image developing toner including resin fine particles containing a crystalline polymer and an amorphous polymer, wherein the amorphous polymer and the crystalline polymer are represented by the following formula (1): Is a toner for developing an electrostatic charge image.
(Formula 1) δa−δc ≧ 1.05 [(cal / ml) ^1/2 / 25 ° C.]
Where δa is the solubility parameter of the amorphous polymer
δc: solubility parameter of crystalline polymer

<2> The electrostatic charge image developing toner according to <1>, wherein the crystalline substance has a melt viscosity at (melting point + 20) ° C. of 10 Pa · S or more and 10,000 Pa · S or less.
<3> The resin fine particles are prepared by mixing the crystalline polymer and the radical polymerizable monomer that forms the amorphous polymer, preparing a mixture, and then emulsifying and dispersing the mixture in an aqueous medium. The electrostatic charge image developing toner according to <1>, wherein the toner is resin fine particles obtained by polymerizing the radical polymerizable monomer.

<4> The electrostatic image developing toner according to <3>, wherein the radical polymerization is polymerization by a miniemulsion method.
<5> At least one component of the amorphous polymer is a radically polymerizable unsaturated acid monomer having a water solubility at 25 ° C. of 80 [g / 100 g-H ₂ O] or less, and / or The toner for developing an electrostatic charge image according to <1>, which contains a polymer obtained by copolymerizing the acid anhydride.

<6> The radically polymerizable unsaturated acid monomer and acid anhydride are at least one selected from fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, or derivatives thereof. <6> The electrostatic image developing toner according to <5>, wherein the toner is a kind of monomer.
<7> A method for producing an electrostatic charge image developing toner according to <1>, wherein the resin fine particles containing the crystalline polymer and the amorphous polymer are contained in an aqueous medium. And a resin fine particle dispersion in which at least the fused resin fine particles are dispersed, and a colorant dispersion in which a colorant is dispersed, and the resin fine particles and the colorant are adjusted to a toner particle size in an aqueous medium. And a step of heating and fusing the obtained aggregates together, and a method for producing an electrostatic charge image developing toner.

<8> An electrostatic charge image developer comprising a toner and a carrier, wherein the toner is the electrostatic charge image developing toner according to <1>.
<9> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a toner image is formed by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. An image development process, a transfer process for transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target, and a fixing process for thermally fixing the toner image transferred to the surface of the transfer target. In the forming method, the toner for developing an electrostatic charge image according to <1> is used as the toner.

  According to the present invention, there are provided a toner for developing an electrostatic image having excellent particle size distribution characteristics and charging characteristics, a method for producing the same, a developer for developing an electrostatic image using the toner for developing an electrostatic image, and an image forming method. can do.

<The toner for developing an electrostatic charge image of the present invention and the method for producing the toner for developing an electrostatic charge image of the present invention>
The electrostatic image developing toner of the present invention (hereinafter sometimes referred to as “the toner of the present invention”) is an electrostatic image developing toner containing resin fine particles containing a crystalline polymer and an amorphous polymer. The toner for developing an electrostatic charge image, wherein the amorphous polymer and the crystalline polymer satisfy a relationship of the following formula (1).
In the present invention, the “crystalline polyester resin” refers to a resin having a clear endothermic peak rather than a step-like endothermic amount change in differential scanning calorimetry (DSC). In the case of a polymer obtained by copolymerizing other components with respect to the crystalline polyester main chain, when the other components are 50% by mass or less, this copolymer is also called crystalline polyester.
(Formula 1) δa−δc ≧ 1.05 [(cal / ml) ^1/2 / 25 ° C.]
Where δa is the solubility parameter of the amorphous polymer
δc: solubility parameter of crystalline polymer

In the toner of the present invention, in order to achieve sufficient low-temperature fixing characteristics, it is necessary to contain a crystalline component as a toner composition, and charging characteristics without impairing the low-temperature fixing characteristics of the crystalline polymer, In order to improve the particle size distribution characteristics, an amorphous polymer material is further contained, and a fusion technique of a crystalline polymer and an amorphous polymer material is required.
In this case, the compounding ratio of the crystalline polymer material and the amorphous polymer material (crystal crystalline polymer material: amorphous polymer material, mass ratio) is preferably 50:50 to 90:10, and 60:40 -80: 20 is more preferable, and 70: 30-75: 25 is still more preferable.
If the blending ratio of the crystalline polymer material and the amorphous polymer material is in the range of 50:50 to 90:10, the charging property and the particle size distribution property are improved without impairing the low-temperature fixing property. The effect becomes more remarkable.

Thus, in the case of containing a crystalline polymer, how to effectively draw the improvement effect of the amorphous polymer is a further important point in this technology. In particular, the toner charging characteristics mainly depend on the physical and electrical characteristics of the toner particle surface and the vicinity of the surface, so how can the amorphous polymer material be positioned in the particle surface layer and the vicinity thereof? It was an important technical issue.
In the present invention, as a result of diligent research on this technical problem, resin fine particles containing a crystalline polymer and an amorphous polymer are fused in an aqueous medium and further fused. Toner particle formation including fine particles is performed. At this time, by controlling the difference in hydrophilicity between the crystalline polymer and the amorphous polymer to be used in the aqueous medium, that is, the difference in solubility parameter between the crystalline polymer and the amorphous polymer in a specific region, It has been found that sufficient charging characteristics can be obtained as a toner using a polymer, and that excellent particle size distribution characteristics can be achieved in toner production in an aqueous medium. This is presumably because the amorphous polymer is located in the surface layer of the resin fine particles and in the vicinity thereof by controlling the difference in solubility parameter between the crystalline polymer and the amorphous polymer in a specific region.

  Further, as toner particle formation including fused resin fine particles in an aqueous medium, a dispersion of at least fused resin fine particles is prepared, and aggregation and fusion are performed in the aqueous medium. For example, a method using an emulsion polymerization aggregation method disclosed in Japanese Patent No. 3107062 can be mentioned.

At this time, the difference in solubility parameter between the crystalline polymer and the amorphous polymer is controlled in a specific region, but in the present invention, the most versatile method for calculating the solubility parameter between the crystalline polymer and the amorphous polymer. A method proposed by Fedors et al., Which is widely spread and recognized for its usefulness, that is, a method for determining the sum of cohesive energy Δe _i and the sum of molecular volumes Δv _i per unit functional group, and obtaining from the relaxation. (R.F. Fedors, Polym. Eng. Sci., 14, 147 (1974)).
In the polymer of the present invention, each mass fraction is calculated from the actual blending amount of the monomer components used in the polymerization, and each polymerization component is incorporated into the polymer chain at the mass fraction charged. As shown in the following (Formula 2), the solubility parameter of each polymerization unit calculated from each monomer component unit is obtained, and the sum of those values multiplied by the respective weight fractions is calculated. The solubility parameter of the polymer was used. The solubility parameter in the present invention is a solubility parameter at 25 ° C., and is described in, for example, the above-mentioned (RF Fedors, Polym. Eng. Sci., 14, 147 (1974)).

Where δ _overall is the solubility parameter of the polymer [(cal / ml) ^1/2 / 25 ° C]
w _i : Mass fraction calculated from each monomer Δe _i : Sum of cohesive energy per unit functional group of each monomer component (cal / mol)
Δv _i : Sum of molecular volume per unit functional group (cc / mol / 25 ° C)

In the present invention, in order to achieve sufficient charging characteristics and particle size distribution as a toner, δc of the amorphous polymer is crystallized in the solubility parameter (δc) of the crystalline polymer and the solubility parameter (δa) of the amorphous polymer. It is necessary to have a value larger than that of the functional polymer and the difference (δa−δc) to be 1.05 [(cal / ml) ^1/2 / 25 ° C.] or more. If this difference is smaller than 1.05, sufficient charging characteristics and particle size distribution characteristics as a toner cannot be obtained. The (δa−δc) is preferably 1.1 or more, and more preferably 1.15 or more.
The (δa−δc) is more preferably 1.05 or more from the viewpoint of image quality characteristics such as toner scattering. Moreover, it is preferable that it is 2.0 or less.

  The toner of the present invention preferably has a melt viscosity value of 10 Pa · S or more and 10,000 Pa · S or less at (melting point + 20 ° C.) of the crystalline polymer to be used from the viewpoint of further improving the low-temperature fixing characteristics. More preferably, it is 10 Pa · S or more and 1000 Pa · S or less. When the value of the melt viscosity at the above (melting point + 20 ° C.) is less than 10 Pa · S, the crystalline resin and the amorphous polymer are compatible, and the effect of the sharp melt property of the crystalline resin is sufficiently exhibited. You may not be able to. On the other hand, if the value of the melt viscosity at (melting point + 20 ° C.) exceeds 10,000 Pa · S, it becomes difficult to form an emulsion and transfer efficiency to paper or the like may be reduced.

  As described above, a dispersion of fused resin fine particles is prepared and agglomerated and fused in an aqueous medium to produce toner particles. To produce the toner particles, an emulsion polymerization aggregation method is used. Is preferably used, and it is necessary to adjust resin fine particles dispersed in an aqueous medium. In this case, in order to achieve an important characteristic for end use such as high image quality, the toner central particle diameter is preferably 10 μm or less, more preferably 7 μm or less. Further, the volume average particle size distribution of the toner is preferably 1.35 or less, and more preferably 1.30 or less.

  In order to achieve such a preferable toner form, the emulsion polymerization aggregation method is optimal, but even in that case, the resin microparticles, which are one of the toner raw materials in the present invention, have an average particle diameter of 1 μm or less. The particle size is preferred. In this case, as described in the above-mentioned existing technology, it is very difficult to emulsify and disperse the crystalline polymer used in the present invention in an aqueous medium with a mechanical share. It becomes a problem.

In the present invention, for this problem, the crystalline polymer and a radical polymerizable monomer that forms the amorphous polymer by polymerization are mixed to prepare a mixture, and then the mixture is mixed. Is preferably emulsified and dispersed in an aqueous medium to polymerize the radical polymerizable monomer.
Furthermore, after the mixture of the radically polymerizable monomer and the crystalline polymer is emulsified and dispersed in an aqueous medium, polymerization can be performed by the miniemulsion method described later to produce the resin particles most efficiently required. Is preferable in that it is possible.

In addition, in order to control the solubility parameter of the amorphous polymer, the radically polymerizable unsaturated acid monomer whose at least one component has a solubility in water at 25 ° C. of 80 [g / 100 g-H ₂ O] or less. The body and / or its anhydride are preferably copolymerized. in this case,
When the degree of solubility in water at 25 ° C. exceeds 80 [g / 100 g-H ₂ O], when polymerizing by the mini-emulsion method, rather than co-polymerizing in fine particles in view of the polymerization mechanism However, it may become a water-soluble polymer, and it may be difficult to copolymerize as an amorphous polymer in the fine particles. In addition, if these water-soluble polymers remain in a state where they are finally attached to the toner surface, the toner is highly dependent on the environment of charging, which may cause charging abnormalities and significantly deteriorate image quality characteristics. That is, by regulating the solubility of these monomer components in water, the generation of water-soluble polymer components or oligomers can be suppressed as much as possible.
The solubility of the at least one component in water at 25 ° C. is preferably 0 to 50 [g / 100 g-H ₂ O]. In the present invention, since the solubility in water is preferably as low as possible, the lower limit is naturally zero.

In that case, particularly preferable monomers include fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and derivatives thereof, and these can be used alone or in combination. Furthermore, in the case of these acid anhydrides, it is known that a part or all of them are hydrolyzed to become an acid during the polymerization, and after the polymerization, an appropriate hydrolysis can be carried out by a known method using an acid, an alkali or the like. It is possible to do.
The present invention will be described in further detail below.

(Crystalline polymer)
Examples of the crystalline polymer in the resin fine particles include polyester, polyamide, polyimide, and the like, which are obtained by reacting an aliphatic diol with an aliphatic dicarboxylic acid (including acid anhydride and acid chloride). Aliphatic polyamides obtained by reacting aliphatic polyesters and aliphatic diamines with aliphatic dicarboxylic acids (including acid anhydrides and acid chlorides) are preferred, and aliphatic polyesters are particularly preferred.

  The crystalline polyester resin is synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. Examples of the divalent carboxylic acid component include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12 -Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid Aromatic dicarboxylic acids such as dibasic acids such as, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  In addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above, a dicarboxylic acid component having a sulfonic acid group can also be used as the acid component. In the case of the present invention, it is preferable to reduce the solubility parameter of the crystalline polymer. Therefore, the dicarboxylic acid having a sulfonic acid group has a solubility parameter defined as necessary, such as good dispersibility of a coloring material such as a pigment. It is necessary to use it while considering the amount. Examples of the dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned.

  Furthermore, in addition to the above-mentioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond can also be contained. A dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing in that it can be radically cross-linked through the double bond. Examples of such dicarboxylic acids include, but are not limited to, maleic acid, fumaric acid, 3-hexenedioic acid, and 3-octenedioic acid. In addition, these lower esters, acid anhydrides and the like are also included. Among these, fumaric acid, maleic acid and the like are preferable from the viewpoint of cost.

  On the other hand, the polyhydric alcohol component is preferably an aliphatic diol, and more preferably a linear aliphatic diol having 2 to 20 carbon atoms in the main chain portion. When the aliphatic diol is branched, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. Moreover, when the number of carbon atoms exceeds 20, it is difficult to obtain practical materials. The carbon number is more preferably 14 or less. Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 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- Examples include, but are not limited to, tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type and may use 2 or more types together.

(Amorphous polymer)
As the amorphous polymer used in the present invention, an amorphous polymer derived from polycondensation, polyaddition polymerization, addition condensation polymerization, addition polymerization or the like such as the above-mentioned polyester resin can be used, but the most preferable. Examples of the form include non-crystalline polymers derived from radical polymerization among addition polymerization.
As the monomer to be radically polymerized (radical polymerizable monomer), an aromatic vinyl monomer, an acrylate ester monomer, a methacrylate ester monomer, a vinyl ester monomer, Examples include vinyl ether monomers, monoolefin monomers, diolefin monomers, and halogenated olefin monomers.

In addition, a radical polymerizable monomer having an acidic group or an acid anhydride thereof, a radical polymerizable monomer having a basic group, or an acrylate or methacrylate of a polyalkylene glycol having a hydroxyl terminal can be used. As described above, it is preferable that these acidic groups and acid anhydrides are at least one component of the copolymer component as the most preferable form, and in this case, the solubility in water at 25 ° C. is 80 [g / 100 g-H ₂ O. The following are preferred. Particularly preferred monomers include fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride and derivatives thereof.

  Examples of the aromatic vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2 Styrene monomers such as 1,4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.

  Examples of the acrylate ester monomer and methacrylate ester monomer include methyl acrylate, ethyl acrylate, butyl acrylate, acrylate-2-ethylhexyl, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, Examples include ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. It is done.

  Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl benzoate. Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

  Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like. Examples of the halogenated olefin monomer include vinyl chloride, vinylidene chloride, vinyl bromide and the like.

(Resin fine particles)
The method for producing resin fine particles containing a crystalline polymer and an amorphous polymer in the present invention is produced by a step of fusing the resin fine particles containing the crystalline polymer and the amorphous polymer in an aqueous medium. As the step of fusing, for example, a prepolymerized crystalline polymer is emulsified and dispersed in an aqueous medium, a desired amorphous polymer monomer is added to the crystalline polymer emulsion, and a seed polymerization method is performed. , Multi-stage swelling method (Advanced in Polymer Polymer Science, 13, 101, 1980) can be used. However, the important point is that the main polymerization field is not a polymerization field mainly through a normal micelle, but a crystalline property. It is preferable that polymerization is carried out mainly in the polymer emulsified particles via normal micelles. Furthermore, it is possible to use a technique in which a crystalline polymer and an amorphous polymer are polymerized in advance and then mixed and emulsified in an aqueous medium. In these cases, in order to obtain submicron particles of 1 μm or less as described above. Requires large mechanical and thermal energy. Further, for the purpose of reducing energy, a method of mixing an organic solvent with a crystalline or / and amorphous polymer and emulsifying and dispersing it can be applied, but there is a problem in handling in terms of environment.

  In the case of the present invention, the most preferable method is the following miniemulsion method. This is because a water-soluble or oil-soluble initiator is prepared by emulsifying an oil layer (polymerization layer) containing at least a monomer capable of radical polymerization to about 5 microns or less, preferably 1 micron or less, more preferably 0.7 microns or less. Is a method of polymerizing a radical polymerizable monomer to obtain polymer fine particles. In this case, the polymerization field is in a monomer droplet emulsified in advance (a polymerizable monomer emulsion previously emulsified). Furthermore, in recent years, there are cases where the miniemulsion method is further finely classified into microemulsions, miniemulsions, microemulsions, etc., in terms of droplet sizes that are initially dispersed. It is defined as 5 μm or less, preferably 1 μm or less, and more preferably 0.7 μm or less. Hereinafter, the polymerization method will be described in more detail.

  First, the crystallized resin and a radical polymerizable monomer that forms an amorphous polymer are mixed. After melting, the crystalline resin is mixed with a radical polymerizable monomer that forms an amorphous polymer. At this time, the two may be completely dissolved, but the polymer composition needs to exhibit a desired solubility parameter difference when the radical polymerization is completed. The combination of the crystalline resin and the various amorphous polymers described above including the radical polymerizable polymer need not be one kind, and a plurality of molecular weights or kinds can be used. In addition to radically polymerizable monomers, additives such as a chain transfer agent and a crosslinking agent that control polymerization can also be used. In addition to this, it is possible to mix elements (coloring material, release agent, etc.) constituting the toner at this time. In order to further lower the resin viscosity at the time of emulsification, a solvent insoluble in water such as toluene and ketone can be used, but this is not preferable in view of environmental load.

  The mixture thus obtained is emulsified and dispersed in an aqueous medium. Examples of a method for dispersing in an aqueous medium include a method using shear, a method using collision, a method using vibration, and the like, and a method using a shearing force is preferable. Specifically, a method of dispersing using mechanical energy is preferable, and as an apparatus used therefor, ultra turrax, claremix, optimizer, gorin homogenizer, ultrasonic disperser, planetary ball mill, microdisperser, cavitron Etc.

  An emulsification aid may be used in the aqueous medium. Examples of the emulsification aid include a surfactant that lowers the interfacial tension at the resin interface and promotes emulsified particles, a surfactant that assists the adsorption of the surfactant, and an emulsion stabilizer that prevents reunion of the emulsified particles. be able to.

  Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  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, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, dialkyl Sodium sulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, capro Sodium, potassium stearate, and the like calcium oleate.

  Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters.

  In the miniemulsion method, usually, higher alcohols typified by heptanol and octanol, and higher aliphatic hydrocarbons typified by hexadecane are often blended as a stabilizing aid in order to prevent the Ostwald Ripping phenomenon.

As the emulsion stabilizer, the above-mentioned nonionic surfactant is often used as an emulsion stabilizer.
An acid or alkali can also be used for adjusting the pH of the resin. This pH is preferably in the range of pH 7 ± 2. If the acidity or alkalinity is too high, the resin may be hydrolyzed.
Examples of the pH adjuster used here include a water-soluble acid or alkali.
Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, perchloric acid, carbonic acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, magnesium hydroxide and the like.

  Next, the obtained emulsion is polymerized. As an advantage of polymerizing the emulsion emulsified and dispersed in an aqueous medium, the viscosity at the time of emulsification of the crystallized resin can be lowered, the ratio of the crystalline resin can be increased compared to general emulsion polymerization, and amorphous For example, it is possible to produce a latex of a uniform crystallized resin and a radical polymerizable monomer, which can provide emulsion stability equivalent to that of a polymer. Further, the formation of a latex of a uniform crystallized resin and a radical polymerizable monomer has a good effect on the distribution of the crystallized resin and the amorphous polymer in the toner after the aggregation and coalescence steps.

  As the polymerization method, a known polymerization method such as a method using a radical polymerization initiator, a method using ultraviolet irradiation, heat or the like can be adopted, but a method using a radical initiator is preferred. There are oil-soluble and water-soluble radical polymerization initiators, but both initiators can be used.

  Examples of the radical polymerization initiator include ammonium persulfate, potassium persulfate, sodium persulfate, 2,2′-azobis- [2-methylpropionamide] -dihydrochloride, t-butylperoxy-2-ethylhexa Noate, cumyl perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2 , 2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4 -Methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butyl) Peroxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylper) Oxy) octane,

n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5- Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylper) Oxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di -T-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5 Di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) Silane, 2,2′-azobis (2-methylpropionamidine dihydrochloride), 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 4,4′-azobis (4 -Cyanovaleric acid) and the like.

Next, a method for producing the toner for developing electrostatic charge of the present invention (hereinafter sometimes referred to as “the method for producing the toner of the present invention”) will be described in detail.
The toner production method of the present invention comprises a step of fusing resin fine particles containing the crystalline polymer and the amorphous polymer in an aqueous medium, and a resin fine particle dispersion in which at least the fused resin fine particles are dispersed. And a step of mixing the colorant dispersion in which the colorant is dispersed, aggregating the resin fine particles and the colorant to a toner particle diameter in an aqueous medium, and heating and fusing the obtained aggregate. To do.
In the toner production method of the present invention, for example, the fused resin fine particles described above are mixed with a colorant particle dispersion and a release agent particle dispersion, and have a polarity opposite to that of the ionic surfactant. Aggregated particles having a toner diameter are formed by causing heteroaggregation with an ionic surfactant, and then heated to a temperature equal to or higher than the glass transition point of the resin fine particles to fuse and coalesce the aggregated particles, and wash and dry. Can be obtained. The toner shape is preferably from irregular to spherical. As the flocculant, an inorganic salt and a divalent or higher-valent metal complex can be suitably used in addition to the surfactant having the opposite polarity. In particular, the use of a metal complex is preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  In the initial stage of mixing the fused resin fine particles, the colorant particle dispersion, and the release agent particle dispersion in the agglomeration step, the balance of the amount of the ionic dispersant of each polarity is shifted in advance. Then, a polymer of an inorganic metal salt such as polyaluminum chloride is added and ionically neutralized, and then the first-stage base aggregated particles are formed at a temperature not higher than the glass transition point and stabilized. As a step, a resin fine particle dispersion treated with an ionic dispersant of a polarity and quantity that compensates for ionic balance deviation is added, and if necessary, it is contained in the resin fine particles and additional resin fine particles in the aggregated particles Slightly heated below the glass transition point of the resin, stabilized at a higher temperature, and then heated above the glass transition point to adhere the particles added in the second stage of agglomeration to the surface of the base aggregated particles The Or it may be those obtained by coalescence while. Further, the stepwise operation of aggregation may be repeated a plurality of times. This two-stage method is effective for improving the inclusion of the release agent and the colorant.

  The colorant used in the colorant particle dispersion is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, thermal black, bengara, bitumen, titanium oxide, etc. Inorganic pigments, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para-brown and other azo pigments, copper phthalocyanine, metal-free phthalocyanine and other phthalocyanine pigments, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red And condensed polycyclic pigments such as dioxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. And various pigments such as CI Pigment Blue 15: 3. These may be used alone or in combination of two or more.

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

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

  As the aggregating agent, a surfactant having a polarity opposite to that of the surfactant used for the dispersant, an inorganic metal salt, and a metal complex having a valence of 2 or more can be preferably used. Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

  In the fusion step, under the same agitation as in the agglomeration step, the pH of the suspension of the adhered agglomerated particles is set in the range of 6.5 to 8.5 to stop the agglomeration, and then the binder resin The adhered aggregated particles are fused by heating at a temperature above the glass transition point. There is no problem if the heating temperature at the time of fusion is not less than the glass transition point of the binder resin contained in the aggregated particles. The heating time may be performed to such an extent that the surface of the aggregated particles is tanned by fusion, and may be performed for about 0.5 to 1.5 hours. If it takes more time, the crystalline polyester contained in the core aggregated particles is likely to be exposed on the toner surface. This is effective for fixing property and document storage property, but adversely affects the charging property, so that it is not preferable to expose the crystalline polyester to the toner surface.

  The fused particles obtained by fusing can be made into toner particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process. In this case, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to sufficiently wash in the washing step.

  In the drying process, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, or a flash jet method can be adopted. The toner particles are preferably adjusted to have a moisture content after drying of 1.0% or less, preferably 0.5% or less.

  As described above, various known external additives such as inorganic fine particles and organic fine particles as described above can be added to the toner particles granulated through the drying step as described above according to the purpose.

  As inorganic fine particles as external additives, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth , Cerium chloride, bengara, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, silicon nitride and the like. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable. Inorganic fine particles are generally used for the purpose of improving fluidity. Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

  When the toner of the present invention is used as a magnetic toner, magnetic powder may be contained in the binder resin. As such magnetic powder, a substance magnetized in a magnetic field is used. Specifically, ferromagnetic powders such as iron, cobalt and nickel, or compounds such as ferrite and magnetite can be used. In particular, in the present invention, in order to obtain toner in the aqueous layer, it is necessary to pay attention to the water layer transferability of the magnetic material, and it is preferable to perform surface modification, for example, hydrophobization treatment.

<Developer for developing electrostatic image>
The developer for developing an electrostatic image of the present invention is an electrostatic image developer containing a toner and a carrier, and the toner is the toner for developing an electrostatic image of the present invention described above. The electrostatic image developing toner of the present invention described above may be used as it is as a one-component developer, but may be used as a two-component developer. When used as a two-component developer, the toner of the present invention is used. Used in combination with carrier.

  There is no restriction | limiting in particular as a carrier which can be used for a two-component developer, A well-known carrier can be used. Examples thereof include magnetic metals such as iron oxide, nickel and cobalt, magnetic oxides such as ferrite and magnetite, resin-coated carriers having a resin coating layer on the surface of the core material, and magnetic dispersion carriers. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

  Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic. Examples thereof include, but are not limited to, acid copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, polyesters, polycarbonates, phenol resins, epoxy resins and the like.

Examples of the conductive material include metals such as gold, silver and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. It is not limited.
Examples of the core material of the carrier include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, in order to use the carrier for the magnetic brush method, it is a magnetic material. It is preferable. The volume average particle size of the core material of the carrier is preferably 10 to 500 μm, and more preferably 30 to 100 μm.

Moreover, in order to coat | cover resin on the surface of the core material of the said carrier, the method of coat | covering with the said coating resin and the coating layer formation solution which melt | dissolved various additives in the appropriate solvent as needed is mentioned. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. And a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater and the solvent is removed in a kneader coater.
The mixing ratio (mass ratio) of the toner of the present invention and the carrier in the two-component developer is preferably in the range of toner: carrier = 1: 100 to 30: 100, preferably about 3: 100 to 20: 100. A range is more preferred.

<Image forming method>
The image forming method of the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step for forming a toner image, a transfer step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing for thermally fixing the toner image transferred to the surface of the transfer target. In the image forming method including the steps, the toner for developing an electrostatic charge image of the present invention described above is used as the toner.
The developer may be either a one-component system or a two-component system. In addition, each of the above steps can use a known step in the image forming method. The image forming method of the present invention may include steps other than the steps described above.

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

In the toner of the present invention (including those contained in the two-component developer, the same applies hereinafter), when the binder resin has a cross-linked structure, it is excellent in releasability due to its effect and the amount of the release agent used. Fixing can be carried out without reducing or using a release agent.
The release agent supplied to the fixing member is preferably not used from the viewpoint of eliminating the adhesion of oil to the transfer target and image after fixing. However, when the supply amount of the release agent is 0 mg / cm ^2. When the fixing member and a transfer medium such as paper are in contact with each other during fixing, the amount of wear of the fixing member may increase and the durability of the fixing member may decrease. It is preferable that a small amount of the release agent is supplied to the fixing member in a range of 8.0 × 10 ⁻³ mg / cm ² or less.
If the supply amount of the release agent supplied to the fixing member exceeds 8.0 × 10 ⁻³ mg / cm ² , the image quality deteriorates due to the release agent adhering to the image surface after fixing, and particularly OHP. Such a phenomenon may appear remarkably when using transmitted light such as. Further, the adhesion of the release agent to the transfer target becomes remarkable, and stickiness may occur. Further, the larger the supply amount of the release agent, the larger the capacity of the tank for storing the release agent, which may increase the size of the fixing device itself.

The release agent supplied to the fixing member is not particularly limited, and examples thereof include liquid release agents such as modified oils such as dimethyl silicone oil, fluorine oil, fluorosilicone oil, and amino-modified silicone oil. Among these, modified oils such as amino-modified silicone oil are preferable because they are adsorbed on the surface of the fixing member and can form a homogeneous release agent layer, because they have excellent wettability to the fixing member. Further, from the viewpoint of forming a homogeneous release agent layer, fluorine oil and fluorosilicone oil are preferable.
The use of fluorine oil or fluorosilicone oil as the release agent supplied to the fixing member does not use the toner of the present invention. In the conventional image forming method, the supply amount of the release agent itself is reduced. However, when the electrophotographic toner of the present invention is used, the supply amount of the release agent can be drastically reduced, so that there is no practical problem in terms of cost.

  There is no particular limitation on the method for supplying the release agent supplied to the fixing member to the surface of the roller or belt, which is a fixing member used for thermocompression bonding. For example, a pad using a pad impregnated with a liquid release agent Examples include a method, a web method, a roller method, a non-contact shower method (spray method), and the like. Among these, a web method and a roller method are preferable. These methods are advantageous in that the release agent can be supplied uniformly and it is easy to control the supply amount. In order to supply the release agent uniformly to the entire fixing member by the shower method, it is necessary to use a separate blade or the like.

The supply amount of the release agent supplied to the fixing member can be measured as follows. That is, when a normal paper (typically a copy paper manufactured by Fuji Xerox Co., Ltd., trade name J paper) used in a general copying machine is passed through a fixing member supplied with a release agent on its surface. The release agent adheres to the plain paper. The attached release agent is extracted using a Soxhlet extractor.
Here, hexane is used as the solvent.
By quantifying the amount of the release agent contained in the hexane with an atomic absorption analyzer, the amount of the release agent adhering to the plain paper can be quantified. This amount is defined as the amount of release agent supplied to the fixing member.

Examples of the transfer target (recording material) to which the toner image is transferred include plain paper, OHP sheet, and the like used in electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer object is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.
Since the image forming method of the present invention uses the developer containing the toner of the present invention, low-temperature fixing is possible and the toner can maintain an appropriate triboelectric charge amount. Therefore, it is excellent in energy saving at the time of image formation, and a good image can be formed while preventing the occurrence of toner scattering and the like.

Hereinafter, the present invention will be specifically described as examples. However, the present invention is not limited to these examples.
(Synthesis of crystalline resin)
Preparation of crystalline polyester resin (1) In a three-necked flask, 10 mol of 9-nonanediol and 9.25 mol of 1,10-dodecanoic acid, 0.75 mol of 5-t-butylisophthalic acid and catalyst Ti (OBu) ₄ (in the acid component) On the other hand, 0.014% by mass) was added, and the air in the container was depressurized by a depressurization operation, and further an inert atmosphere was established with nitrogen gas, followed by refluxing at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the unreacted monomer was removed by distillation under reduced pressure, the temperature was gradually raised to 220 ° C., the mixture was stirred for 12 hours, and when it became viscous, the molecular weight was confirmed by GPC. A polyester resin (1) of 24000 (HLC-8 120GPC, converted by styrene standard substance manufactured by Tosoh Corporation) was obtained. As a result of measuring the thermal characteristics of the obtained polyester resin (1) with a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation: temperature rising rate 3 ° C./min), it had a melting point of 74 ° C. The resin viscosity was 1.2 × 10 ² Pa · S when the viscosity was measured under the measurement condition: (melting point + 20) ° C. using “(device name) ARES” (manufactured by Rheometrics).

Preparation of crystalline polyester (2) In a three-necked flask, 10 mol of 9-nonanediol and 1,10-dodecanoic acid, 9.05 mol, 0.75 mol of 5-t-butylisophthalic acid and sodium dimethyl-5-sulfonate 0 2 mol and catalyst Ti (OBu) ₄ (0.014% by mass with respect to the acid component), and then the pressure in the container is reduced by a pressure reduction operation, and the atmosphere is made inert with nitrogen gas. The mixture was refluxed at 180 ° C. for 6 hours with stirring. Thereafter, the unreacted monomer component was removed by distillation under reduced pressure, the temperature was gradually raised to 220 ° C., the mixture was stirred for 12 hours, and when it became a viscous state, the molecular weight was confirmed by GPC. Crystalline polyester (2) was obtained. As a result of measuring the thermal characteristics of the obtained polyester resin (2) with a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation: temperature rising rate 3 ° C./min), it had a melting point of 75 ° C. The viscosity of the resin was 1.5 × 10 ² Pa · S when measured under the measurement condition (melting point + 20) ° C. using “(device name) ARES” (manufactured by Rheometrics).

Preparation of crystalline polyester (3) In a three-necked flask, 10 mol of 9-nonanediol and 1,10-dodecanoic acid, 9.25 mol, 0.75 mol of 5-t-butylisophthalic acid and dimethyl-5-sulfonic acid sodium salt 1 0.0 mol and catalyst Ti (OBu) ₄ (0.014% by mass with respect to the acid component) were added, and then the air in the container was depressurized by a depressurization operation, and an inert atmosphere was established with nitrogen gas. The mixture was refluxed at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the unreacted monomer was removed by distillation under reduced pressure, the temperature was gradually raised to 250 ° C., the mixture was stirred for 12 hours, and when it became a viscous state, the molecular weight was confirmed by GPC. Crystalline polyester (3) was obtained. As a result of measuring the thermal characteristics of the obtained polyester resin (3) with a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation: temperature rising rate 3 ° C./min), it had a melting point of 74 ° C. The resin viscosity was 1.1 × 10 ² Pa · S when the viscosity was measured at “(melting point + 20) ° C. using“ (device name) ARES ”(manufactured by Rheometrics).

Production of Resin Fine Particles Containing Crystalline Resin and Amorphous Polymer Production of Resin Fine Particle (1) 600 g of crystalline polyester resin (1) is heated to 100 ° C. and melted, styrene: 350 g, n-butyl acrylate: 35 g, Add to a mixed solution of maleic acid (unsaturated acid monomer): 5 g, dodecanethiol: 24 g, hexadecane 10 g and stir well. To this mixture, 50 g of dodecylbenzenesulfonic acid, 9 L of ion-exchanged water and an appropriate amount of 5% -NH ₄ OH aqueous solution as an aqueous medium are added and heated to 90 ° C. The emulsifier used was a combination of “CLEAMIX” (manufactured by M Technique) with a pressurized sealed circulating layer. The aqueous medium and the crystalline resin mixed monomer were put into the circulating layer, and sent to the CLEARMIX at a flow rate of 1 l / min per minute, and the passed emulsion was returned to the circulating layer. Time is 1 hour, temperature is 120 ° C., rotation speed is 20000 rpm. Emulsified. When the particle diameter of the emulsion was measured, the volume center particle diameter was 0.45 μm (LA-700 particle size measuring machine manufactured by Horiba, Ltd.). 3 L of this emulsion was put into a separable flask equipped with a thermometer, a stirrer, and a condenser, and 1.3 g of ammonium persulfate was dissolved in 10 ml of ion-exchanged water and added thereto, followed by polymerization at 85 ° C. for 6 hours. The amorphous polymer (radical polymerized body) was polymerized to produce a crystalline polyester resin (1) and resin fine particles (1) containing the amorphous polymer.

  The obtained resin fine particles (1) had a volume average particle size of 0.50 μm and a radical polymerization rate determined by gas chromatography of 99.9%. The difference in solubility parameter (δa−δc) between the crystalline polyester resin (1) and the amorphous polymer (radical polymerized product) was 1.16. Table 1 shows the solubility of maleic acid in water at 25 ° C.

Preparation of resin fine particles (2) Preparation of resin fine particles (1) is the same as the preparation of resin fine particles (1) except that maleic acid is changed to the same amount of maleic anhydride (unsaturated acid monomer anhydride). Thus, resin fine particles (2) were produced. The obtained resin fine particles (1) had a volume average particle size of 0.51 μm and a radical polymerization rate determined by gas chromatography of 99.9%. The difference in solubility parameter (δa−δc) between the crystalline polyester resin (1) and the amorphous polymer (radical polymerized product) was 1.17. Table 1 shows the solubility of maleic anhydride in water at 25 ° C.

Preparation of resin fine particles (3) In the preparation of resin fine particles (1), resin fine particles were prepared in the same manner as the preparation of resin fine particles (1) except that maleic acid was changed to the same amount of fumaric acid (unsaturated acid monomer). (3) was produced. The obtained resin fine particles (3) had a volume average particle diameter of 0.49 μm and a radical polymerization rate determined by gas chromatography of 99.9%. The difference in solubility parameter (δa−δc) between the crystalline polyester resin (1) and the amorphous polymer (radical polymerized product) was 1.16. Table 1 shows the solubility of fumaric acid in water at 25 ° C.

Preparation of resin fine particles (4) In the preparation of resin fine particles (1), resin fine particles were prepared in the same manner as the preparation of resin fine particles (1), except that maleic acid was changed to the same amount of itaconic acid (unsaturated acid monomer). (4) was produced. The obtained resin fine particles (4 had a volume average particle size of 0.51 μm and a radical polymerization rate determined by gas chromatography of 99.9%. Further, the crystalline polyester resin (1) and the amorphous polymer ( The difference (δa−δc) in solubility parameter from the radical polymerized product was 1.15, and Table 1 shows the solubility of itaconic acid in water at 25 ° C.

Preparation of resin fine particles (5) Preparation of resin fine particles (1) is the same as the preparation of resin fine particles (1) except that maleic acid is changed to the same amount of itaconic acid anhydride (unsaturated acid monomer anhydride). Thus, resin fine particles (5) were produced. The obtained resin fine particles (5) had a volume average particle diameter of 0.45 μm and a radical polymerization rate determined by gas chromatography of 99.9%. Moreover, the difference (δa−δc) in solubility parameter between the crystalline polyester resin (1) and the amorphous polymer (radical polymerized body) was 1.15. Table 1 shows the solubility of itaconic anhydride in water at 25 ° C.

Preparation of resin fine particles (6) In preparation of resin fine particles (1), the crystalline polyester resin (1) was changed to the same amount of crystalline polyester resin (3), and maleic acid was replaced with the same amount of acrylic acid (unsaturated acid). Resin fine particles (6) were produced in the same manner as in the production of the resin fine particles (1) except that the monomer was changed. The obtained resin fine particles (6) had a volume average particle size of 0.35 μm and a radical polymerization rate determined by gas chromatography of 99.9%. Further, the difference (δa−δc) in solubility parameter between the crystalline polyester resin (3) and the amorphous polymer (radical polymerized body) was 0.84. Table 1 shows the solubility of acrylic acid in water at 25 ° C.

Preparation of resin fine particles (7) In preparation of resin fine particles (1), the crystalline polyester resin (1) was changed to the same amount of crystalline polyester resin (2), and maleic acid was replaced with the same amount of acrylic acid (unsaturated acid). Resin particles (7) were prepared in the same manner as the resin particles (1) except that the monomer was changed to (monomer). The obtained resin fine particles (7) had a volume average particle size of 0.40 μm and a radical polymerization rate determined by gas chromatography of 99.9%. Further, the (δa−δc) value of the solubility parameter of the crystalline polyester resin (2) and the amorphous polymer (radical polymerized body) was 1.02. Table 1 shows the solubility of acrylic acid in water at 25 ° C.

Preparation of mold release agent dispersion: Ester wax (Nippon Yushi Co., Ltd .: WE-2, melting point 65 ° C.): 50 g
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5g
・ Ion exchange water: 200g
The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), then dispersed with a Menton Gorin high-pressure homogenizer (Gorin), and a release agent having an average particle size of 230 nm. A release agent dispersion liquid (release agent concentration: 20% by mass) was prepared.

Preparation of Colorant Dispersion / Cyan Pigment (Daiichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1 kg
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 150 g
・ Ion exchange water: 9kg
A colorant dispersion obtained by mixing, dissolving, and dispersing a colorant (cyan pigment) by dispersing for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). Prepared. The average particle diameter of the colorant (cyan pigment) in the colorant dispersion was 0.15 μm, and the colorant particle concentration was 23% by mass.

Example 1
"Manufacture of toner particles (1)"
・ Resin fine particles (1): 950 g
Colorant dispersion: 22.87g
-Release agent dispersion: 50 g
-Nonionic surfactant (IGEPAL CA897): 0.5g
The above raw materials are put into a 5 L cylindrical stainless steel container, and dispersed and mixed for 30 minutes while applying a shearing force at 8000 rpm by Ultraturrax. Subsequently, 0.14 g of a 10% nitric acid aqueous solution of polyaluminum chloride was added dropwise as a flocculant. At this time, the pH of the raw material dispersion was controlled in the range of 4.2 to 4.5. The pH was adjusted with 0.3N nitric acid or 1N aqueous sodium hydroxide as required.

Thereafter, the raw material dispersion is transferred to a polymerization kettle equipped with a stirrer and a thermometer and heated to promote the growth of the adhered aggregated particles at 40 ° C. When the volume average particle diameter becomes 6.0 μm, the pH is adjusted. After the temperature was raised to 9.0, the temperature was raised to 90 ° C. and held at 90 ° C. for 2 hours, and then the pH was gradually lowered to 6.5, then the heating was stopped and the mixture was allowed to cool. Thereafter, it was sieved with a 45 μm mesh, washed repeatedly with water and then dried with a freeze dryer. As a result of measuring the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter), the result was 6.0 μm and the volume average particle size distribution was 1.22. .
The measurement results of the volume average particle size distribution of the toner particles were evaluated according to the following criteria. The results are shown in Table 1.

[Volume average particle size distribution]
○: Volume average particle size distribution is 1.25 or less.
(Triangle | delta): Volume average particle diameter distribution exceeds 1.25 and is 1.30 or less.
X: Volume average particle size distribution exceeds 1.30.

"Production of toner particles"
To 100 parts of the obtained toner particles (1), 1 part of colloidal silica (manufactured by Nippon Aerosil Co., Ltd., R972) was externally added and mixed using a Henschel mixer to obtain an electrostatic image developing toner. .
"Development and evaluation of developer"
On the other hand, 100 parts of ferrite particles (manufactured by Powdertech Co., Ltd., average particle size 50 μm) and 1 part of methacrylate resin (manufactured by Ryo Rayon Co., Ltd., molecular weight 95000) were placed in a pressure kneader together with 500 parts of toluene and mixed at room temperature for 15 minutes. Thereafter, the temperature was raised to 70 ° C. while mixing under reduced pressure, and toluene was distilled off, followed by cooling and sizing using a 105 μm sieve to produce a ferrite carrier (resin-coated carrier). This ferrite carrier and the electrostatic image developing toner were mixed to prepare a two-component electrostatic image developer having a toner concentration of 7% by mass. As a result of measuring and evaluating the absolute value of the charge amount (μC / g) in an environment of 80% RH and 28 ° C. with respect to this electrostatic charge image developer, the toner charge amount is −35 μC. Good chargeability of / g was exhibited. Further, the image quality characteristics were evaluated using the Docu Center Color 500CP modified machine manufactured by Fuji Xerox Co., Ltd., the fixing temperature, the initial image quality, and the image quality after 10,000 sheets were evaluated and visually evaluated according to the following criteria. The results are shown in Table 1.
The image formation includes a latent image forming step, a developing step, a transfer step, and a fixing step.

[Charging characteristics]
○: Charge amount is −30 μC / g or less.
Δ: Charge amount is more than −30 μC / g and not more than −10 μC / g.
X: Charge amount exceeds −10 μC / g.

[Image quality characteristics]
○: No toner scattering, sufficient image density and uniform image quality were obtained, and good image quality characteristics with no practical problems were obtained.
Δ: Slight scattering of toner was observed, but an image density and a uniform image quality that were not problematic for practical use were obtained.
X: Toner scattering was remarkably observed, and the uniformity of initial image density and image quality was insufficient, which was a practical problem.

(Example 2)
“Preparation of toner particles (2)”
Toner particles (2) were produced in the same manner as in Example 1, except that the resin fine particles (2) were used instead of the resin fine particles (1). The obtained toner particles (2) were measured for the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.). As a result, 5.9 μm, volume average particles The diameter distribution was 1.23.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to the toner particles (2), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount showed a good chargeability of -35 μC / g. Furthermore, the fixing temperature is 100 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

(Example 3)
“Preparation of toner particles (3)”
Toner particles (3) were produced in the same manner as in Example 1, except that the resin fine particles (3) were used instead of the resin fine particles (1). The obtained toner particles (3) were measured for the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.). As a result, 6.0 μm, volume average particles were obtained. The diameter distribution was 1.23.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to toner particles (3), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount showed a good chargeability of -36 μC / g. Furthermore, the fixing temperature is 100 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

Example 4
“Preparation of toner particles (4)”
Toner particles (4) were produced in the same manner as in Example 1, except that the resin fine particles (4) were used instead of the resin fine particles (1). The obtained toner particles (4) were measured for the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter). As a result, 6.1 μm, volume average particles were obtained. The diameter distribution was 1.23.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to toner particles (4), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount showed a good chargeability of -34 μC / g. Furthermore, the fixing temperature is 100 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

(Example 5)
"Preparation of toner particles (5)"
Toner particles (5) were produced in the same manner as in Example 1, except that the resin fine particles (5) were used instead of the resin fine particles (1). The obtained toner particles (5) were measured for volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.). As a result, 6.2 μm, volume average particles were obtained. The diameter distribution was 1.22.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to toner particles (5), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount showed a good chargeability of -37 μC / g. Furthermore, the fixing temperature is 100 ° C., which is possible at an unprecedented low temperature, and there is no scattering of toner as image quality characteristics, and a sufficient image density and uniform image quality are obtained, and good image quality characteristics with no practical problems are obtained.

(Comparative Example 1)
“Preparation of Toner Particles (6)”
In Example 1, toner particles (6) were produced in the same manner as in Example 1, except that the resin fine particles (6) were used instead of the resin fine particles (1). The obtained toner particles (6) were measured for the volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.). As a result, 6.5 μm, volume average particles were obtained. The size distribution was 1.37, and there was a problem in sufficient particle size control and toner particle size distribution controllability.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to toner particles (6), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount was as low as −3 μC / g. Furthermore, the fixing temperature is 100 ° C., and fixing at a lower temperature than before is possible, but toner scattering is noticeably observed as image quality characteristics, and the initial image density and uniformity thereof are insufficient. It was a problem in practical use.

(Comparative Example 2)
“Production of toner particles (7)”
Toner particles (7) were produced in the same manner as in Example 1, except that the resin fine particles (7) were used instead of the resin fine particles (1). The obtained toner particles (7) were measured for volume average particle size of the final toner particles using a Coulter counter [TA-II] type (aperture diameter: 50 μm; manufactured by Coulter, Inc.). As a result, 7.2 μm, volume average particles were obtained. The particle size distribution was 1.38, and there was a problem in sufficient particle size control and toner particle size distribution controllability.

"Developer adjustment and image quality evaluation"
In Example 1, an electrostatic charge image developer was prepared in the same manner as in Example 1 except that the toner particles (1) were changed to toner particles (7), and the same evaluation as in Example 1 was performed. As a result, the toner charge amount was as low as -2 μC / g. Furthermore, the fixing temperature is 100 ° C., and fixing at a lower temperature than before is possible, but toner scattering is noticeably observed as image quality characteristics, and the initial image density and uniformity thereof are insufficient. It was a problem in practical use.

  From Table 1, it can be seen that Examples 1 to 5 are excellent in toner particle size controllability and particle size distribution controllability compared to Comparative Examples 1 and 2, and thus have good particle size distribution characteristics and charging characteristics.

Claims (9)

An electrostatic charge image developing toner comprising resin fine particles containing a crystalline polymer and an amorphous polymer,
The toner for developing an electrostatic charge image, wherein the amorphous polymer and the crystalline polymer satisfy a relationship of the following formula (1).
(Formula 1) δa−δc ≧ 1.05 [(cal / ml) ^1/2 / 25 ° C.]
Where δa is the solubility parameter of the amorphous polymer
δc: solubility parameter of crystalline polymer   2. The electrostatic image developing toner according to claim 1, wherein the crystalline substance has a melt viscosity at (melting point + 20) ° C. of 10 Pa · S or more and 10,000 Pa · S or less.   The resin fine particles are prepared by mixing the crystalline polymer and the radically polymerizable monomer forming the amorphous polymer, preparing a mixture, and then emulsifying and dispersing the mixture in an aqueous medium. 2. The electrostatic image developing toner according to claim 1, wherein the toner is a resin fine particle obtained by polymerizing a monomer capable of radical polymerization.   4. The electrostatic image developing toner according to claim 3, wherein the radical polymerization is polymerization by a mini-emulsion method. At least one component of the amorphous polymer is a radically polymerizable unsaturated acid monomer having a water solubility at 25 ° C. of 80 [g / 100 g-H ₂ O] or less, and / or its acid anhydride. The electrostatic image developing toner according to claim 1, further comprising a polymer obtained by copolymerizing the product.   The radically polymerizable unsaturated acid monomer and acid anhydride are at least one kind selected from fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, or derivatives thereof. The toner for developing an electrostatic charge image according to claim 5, wherein the toner is a toner.   A method for producing an electrostatic image developing toner for producing the electrostatic image developing toner according to claim 1, wherein the resin fine particles containing the crystalline polymer and the amorphous polymer are fused in an aqueous medium. Mixing a resin fine particle dispersion in which at least the fused resin fine particles are dispersed, and a colorant dispersion in which a colorant is dispersed, and aggregating the resin fine particles and the colorant to a toner particle diameter in an aqueous medium, And a step of heating and fusing the obtained aggregates. A method for producing a toner for developing an electrostatic charge image. An electrostatic charge image developer containing toner and carrier,
The electrostatic image developer according to claim 1, wherein the toner is the electrostatic image developing toner according to claim 1.   A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a developing step for 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. And 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 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 1 as the toner.