JP4742936B2 - Toner for developing electrostatic image and method for producing the same - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image used for developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, and a method for producing the same.

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.
As the developer used here, 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 are known. A kneading and pulverizing method is used in which a plastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, and after cooling, is finely pulverized and classified, and has some problems as described below.

  In the ordinary kneading and pulverizing method, the toner shape and the surface structure of the toner are indeterminate, and although it varies slightly depending on the pulverization properties of the materials used and the conditions of the pulverization process, it is difficult to control the intentional toner shape and surface structure. . In the kneading and pulverizing method, the range of material selection is limited. Specifically, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized by an economically possible production apparatus. However, if the resin colorant dispersion is made brittle to satisfy these requirements, finer powder may be generated or the toner shape may be changed due to mechanical shearing force applied in the developing machine.

  Due to these effects, in the two-component developer, the charging deterioration of the developer due to adhesion of fine powder to the carrier surface is accelerated, and in the one-component developer, toner scattering occurs due to the expansion of the particle size distribution. Deterioration in developability due to changes in image quality tends to cause image quality degradation. In addition, when a toner is formed by adding a large amount of a release agent such as wax, exposure to the release agent on the surface is often affected by the combination with a thermoplastic resin. In particular, in the case of a combination of a resin having increased elasticity due to a high molecular weight component and slightly pulverized resin and a brittle wax such as polyethylene or polypropylene, exposure of these wax components is often observed on the toner surface. This is advantageous for releasability at the time of fixing and cleaning of untransferred toner from the photoreceptor, but the polyethylene on the surface layer is easily transferred by mechanical force, resulting in contamination of the developing roll, photoreceptor and carrier. It becomes easy and leads to a decrease in reliability.

  In addition, since the toner shape is irregular, the fluidity may not be sufficient even with the addition of a fluidity aid, and the time-dependent movement of the fine particles on the toner surface due to the mechanical shearing force during use may occur. When the fluidity is lowered or the fluidity aid is buried in the toner, the developability, transferability, and cleaning properties are deteriorated. Further, when the toner collected by cleaning is returned to the developing machine and used again, the image quality is likely to further deteriorate. On the other hand, when the flow aid is further increased in order to prevent these, the generation of black spots on the photoreceptor and the scattering of the aid particles occur.

As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, the surface hardness can be maintained without suppressing the exposure of the release agent to the surface or the fixing property. In addition, it is necessary to improve the mechanical strength of the toner itself and to achieve both sufficient charging and fixing properties.
In recent years, the demand for higher image quality has increased, and in image formation, there has been a significant trend toward toner diameter reduction in order to realize high-definition images.
However, with the simple reduction in size while maintaining the conventional particle size distribution, the presence of fine powder side toner causes significant problems of carrier and photoconductor contamination and toner scattering, making it difficult to achieve high image quality and high reliability at the same time. It is. For this purpose, it is necessary that the particle size distribution can be sharpened and the particle size can be reduced.

In recent years, as means for intentionally enabling control of toner shape and surface structure, a toner production method by emulsion polymerization aggregation (see, for example, Patent Documents 1 and 2), suspension polymerization toner, suspension granulation toner, A wet process toner manufacturing method such as a suspension emulsification aggregation unity toner has been proposed.
These wet process toners are suitable for the production of toner particles having a sharp particle size distribution and small particle diameters. Can be planned.

As a further requirement, in order to reduce the amount of energy used in copying machines and printers, a technology for fixing toner with lower energy is desired, and there is a strong demand for toner for electrophotography that can be fixed at a lower temperature.
As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of a toner resin (binder) is generally performed. However, if the glass transition point is too low, powder aggregation (blocking) is likely to occur, and the toner preservability on the fixed image is lost. is required.

  This glass transition point is a design point of many resin for toners currently on the market, and there is a problem that a toner capable of fixing at a lower temperature cannot be obtained by the method of lowering the glass transition point. Although the fixing temperature can be lowered by using a plasticizer, there is a problem because blocking occurs during storage of the toner or in the developing machine.

  Under such circumstances, as a means for achieving both blocking prevention, image storage stability up to 60 ° C., and low-temperature fixability, a technique using a crystalline resin as a binder constituting the toner can be considered. In order to achieve both, a method using a crystalline resin as a toner has been known for a long time (for example, see Patent Document 3).

  On the other hand, for the purpose of preventing offset (for example, see Patent Document 4) and pressure fixing (for example, see Patent Document 5), a technique using a crystalline resin has been known for a long time. In addition, a technique of applying a polymer having an alkyl group side chain having 14 or more carbon atoms to a toner as a crystalline resin has been proposed (see, for example, Patent Document 6). The melting point of the powder was as low as 62 to 66 ° C., too low, and there was a problem in the reliability of powder and images. Furthermore, the techniques of Patent Documents 4 and 5 have a problem that the fixing performance of the crystalline resin to paper is not sufficient.

  On the other hand, Patent Document 6 further includes a polyester resin as a crystalline resin that is expected to improve the fixability to paper. As a technique for using the crystalline polyester resin in a toner, a glass transition temperature of 40 ° C. A technique for mixing a crystalline polyester resin and a crystalline polyester resin having a melting point of 130 to 200 ° C. has been proposed. However, this technique has excellent pulverization properties and blocking resistance, but has a problem in that the low-temperature fixability cannot be achieved since the crystalline polyester resin has a high melting point.

  Furthermore, a technique for obtaining low-temperature fixing by mixing a low-melting crystalline resin and an amorphous resin and controlling the degree of compatibilization has been proposed (see, for example, Patent Documents 7 and 8). However, the progress of compatibilization between the crystalline resin and the amorphous resin causes plasticization of the mixed resin, which causes a problem that not only blocking resistance but also chargeability deteriorates.

  Polyester resin is used as a binder resin in place of styrene / acrylic resin, which has been widely used, and is excellent in low-temperature fixability and heat-resistant storage, and its use has recently been attempted. However, the polyester resin has a lower dispersibility of the release agent (wax) than the styrene / acrylic resin in the kneading and pulverization method, and is easily pulverized at the interface between the binder resin and the release agent during pulverization. There is a problem that the release agent is exposed to the toner and the toner powder characteristics and charging characteristics are deteriorated. In addition, in the coalescence / fusion coalescence method, which is a wet process, when the coalescence is performed by heating, the release agent is exposed to the toner surface or detached from the toner particles at the same time as the coalescence of the release agent by heat. Therefore, there are problems such as deterioration of toner powder characteristics and charging characteristics.

  Here, as means for improving the dispersibility of the polyester resin and wax in the toner, it is proposed to improve the dispersibility by defining the solubility parameter of the binder resin and wax and the difference in solubility parameter of the binder resin and wax. (For example, see Patent Documents 9 to 13). However, even if these means are used, it is insufficient to suppress the exposure of the wax component to the toner surface, and is insufficient as an effect of suppressing the contamination of the wax component to a member such as a developing roll or a photoreceptor or a carrier. Met.

  Further, as means for enabling control of the toner shape and surface structure, including suppression of exposure of the wax component to the toner surface, a toner production method by emulsion polymerization aggregation method, suspension polymerization method, suspension granulation method, A wet process toner manufacturing method such as a suspension emulsification aggregation method has been proposed (see, for example, Patent Documents 14 and 15). The wet process toner is more preferable because it is suitable for the production of toner particles having a sharp particle size distribution and a small particle diameter, and a high-definition image can be realized in image formation. In particular, in terms of toner surface shape controllability, the agglomerated and coalesced toner is excellent, and can improve the chargeability, durability, and cleaning properties.

  Furthermore, as a means for achieving both blocking prevention, image storage stability, and low-temperature fixability, a technique using a crystalline resin as a binder constituting the toner is considered (see, for example, Patent Documents 16 to 18). A technique using a crystalline resin has been known for a long time for the purpose of preventing offset (for example, see Patent Document 19) and pressure fixing (for example, see Patent Document 20). However, the technique of Patent Document 16 applies a polymer having an alkyl group side chain having 14 or more carbon atoms to the toner, and has a problem in the reliability of powder and images. Further, the crystalline resins described in Patent Documents 17 and 18 have a problem that the fixing performance to paper is not sufficient.

  On the other hand, a polyester resin is cited as a crystalline resin that is expected to improve the fixability to paper, and a technique using the crystalline polyester resin in a toner is described in Patent Document 18. This is a technique in which an amorphous polyester resin having a glass transition temperature of 40 ° C. or higher and a crystalline polyester resin having a melting point of 130 to 200 ° C. are mixed and used. However, this technique has excellent pulverization properties and blocking resistance, but has a problem in that the low-temperature fixability cannot be achieved since the crystalline polyester resin has a high melting point.

  On the other hand, a technique for obtaining low-temperature fixing by mixing a low melting crystalline resin and an amorphous resin and controlling the degree of compatibilization has been proposed (see, for example, Patent Documents 21 and 22). Furthermore, there is a technology that uses a mixture of crystalline polyester and amorphous resin, and prevents blocking between papers during discharge without compromising transparency by compatibilizing the crystalline part due to the temperature history during fixing. It has been introduced (for example, see Patent Document 23). However, the progress of compatibilization of crystalline resin and non-crystalline resin causes plasticization of the mixed resin, and not only blocking resistance, but also the pressure and heat on the image, such as transportation and transportation of printed matter and the interior of the car in summer. When added, the toner image is transferred to the opposite surface, causing a problem of image loss.

As described above, in the electrophotographic process, in order to stably maintain the performance of the toner even under various mechanical stresses, the surface hardness can be maintained without suppressing the exposure of the release agent to the surface or the fixing property. In addition, it is necessary to improve the mechanical strength of the toner itself and to achieve both sufficient charging and fixing properties. In other words, the existing technologies have achieved high reliability such as compatibility between low-temperature fixability and offset, toner storage stability, fixed image storage stability and toner chargeability, and sharpening of the toner particle size distribution accompanying the demand for higher image quality. It has been difficult to satisfy all the problems in the toner manufacturing method suitable for the reduction in size and particle size.
Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Publication No. 63-25335 Japanese Patent Publication No. 56-13943 JP 2004-206081 A Japanese Patent Laid-Open No. 2004-50478 JP 2000-352841 A JP 2000-35695 A Japanese Patent Laid-Open No. 11-38677 JP 2003-25558 A Japanese Patent Laid-Open No. 2003-28024 Japanese Patent Laid-Open No. 63-282275 JP-A-6-250439 Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Publication No. 63-25335 Japanese Examined Patent Publication No.62-39428 Japanese Patent Publication No. 63-25335 JP 2004-206081 A Japanese Patent Laid-Open No. 2004-50478 Japanese Patent Laid-Open No. 2003-50478

  Accordingly, an object of the present invention is to solve the conventional problems and achieve the following object. That is, the present invention provides a toner for developing an electrostatic image that solves the above-mentioned problems in the conventional toner, and a method for producing the same. That is, an object of the present invention is to provide an electrophotographic toner excellent in charging property, fixing property at low temperature, and toner blocking property, and a method for producing the same.

The above problems are solved by the present invention described below.
That is, the present invention
<1> includes a crystalline resin A and amorphous polymer B as a binder resin, the surface of the inorganic amorphous polymer B is coated with a surface layer mainly composed of different amorphous polymer C, further away An electrostatic charge image developing toner comprising a mold agent D, wherein the amorphous polymer B is an amorphous polyester resin B ′, and an endothermic peak temperature TmA [° C.] derived from the crystalline resin A; The endothermic peak TmAB [° C.] derived from the crystalline resin A when the crystalline resin A and the amorphous polymer B are mixed with the crystalline resin A when the crystalline resin A and the amorphous polymer C are mixed. the endothermic peak temperature TMAC [° C.], but meets the following relationship formula (1), and the solubility parameter SP _B of the amorphous polymer B, a solubility parameter SP _D of the releasing agent D, but the following formula ( The endothermic peak temperature of the crystalline resin A satisfying the relationship 3) Is 60 to 80 ° C., and the content of the crystalline resin A is 5 to 50% by mass .
TmAB <TmAC ≦ TmA Formula (1)
_{· 0.8 <SP B - SP D} <1.8 ··· formula (3)

<2> the solubility parameter SP _A of the previous SL crystalline resin A, when the solubility parameter SP _C of the previous SL amorphous polymer C, and satisfy the relationship below following formula (2) <1 >. The toner for developing an electrostatic charge image according to <1>.
_{· SP D <SP A <SP} B <SP C ··· formula (2)

< 3 > In the differential scanning calorimetry curve obtained by the measurement with the differential scanning calorimeter, the endothermic peak derived from the crystalline resin A and the endothermic derived from the release agent D in the temperature range of 50 to 100 ° C. in the first temperature rising process. The sum E of the absolute values of the endothermic amounts of the peaks is greater than the sum F of the absolute values of the endothermic peaks of the endothermic peak derived from the crystalline resin A and the endothermic peak derived from the release agent D in the second temperature rising process after cooling. The toner for developing an electrostatic charge image according to < 1 > or < 2 >, which is large.

<4> prior Symbol softening point of the amorphous polymer B and C is characterized by a 80 to 130 ° C. <1> ~ <3> any one toner der for developing an electrostatic charge image according to the The

< 5 > The toner for developing an electrostatic charge image according to any one of <1> to < 4 >, wherein the crystalline resin A is a crystalline polyester. < 6 > Angular frequency: 1 Hz, 30 The storage elastic modulus GL (30) at 1 ° C. is 1 × 10 ⁷ Pa or more, and the loss elastic modulus GN (90) at 90 ° C. is 1.0 × 10 ⁵ Pa or less. 5 >. The electrostatic charge image developing toner according to any one of 5 >.

< 7 > A method for producing a toner for developing an electrostatic charge image according to any one of <1> to < 6 >, wherein a crystalline resin A fine particle dispersion in which crystalline resin A fine particles are dispersed, and an amorphous An amorphous polymer B fine particle dispersion in which polymer B fine particles are dispersed is mixed to prepare a mixed dispersion, to which one or more kinds of metal salt polymers containing polyaluminum chloride are added, and the mixed dispersion Is formed at a temperature lower than the endothermic peak temperature of the crystalline resin A fine particles when measured with a differential scanning calorimeter, and then an aggregated fine particle dispersion is produced by agglomerating and growing the aggregated particles Amorphous polymer C fine particles dispersed in amorphous polymer C fine particles are added to the agglomerated fine particle dispersion and mixed to add amorphous polymer C fine particles to the surface of the aggregated fine particles. Adhesion process and before It is characterized by having a fusion / union step of stopping the growth of the agglomerated fine particles by heating the aggregated fine particle dispersion by making the pH of the agglomerated fine particle dispersion subjected to the adhesion step basic. And a method for producing a toner for developing an electrostatic image.

  The present invention provides a toner for developing an electrostatic image that solves the above-mentioned problems in the conventional toner and a method for producing the same. That is, the present invention can provide an electrophotographic toner excellent in charging property, fixing property at low temperature, and toner blocking property, and a method for producing the same.

The toner for developing an electrostatic charge image of the present invention contains at least a crystalline resin A and an amorphous polymer B as a binder resin, and the amorphous polymer C whose surface is different from that of the amorphous polymer B as a main component. A toner for developing an electrostatic charge image coated with a surface layer, wherein the endothermic peak temperature TmA [° C.] derived from the crystalline resin A is mixed with the crystalline resin A and the amorphous polymer B. The endothermic peak TmAB [° C.] derived from the crystalline resin A and the endothermic peak temperature TmAC [° C.] derived from the crystalline resin A when the crystalline resin A and the amorphous polymer C are mixed are represented by the following formula (1). It is characterized by satisfying the relationship.
Hereinafter, the electrostatic image developing toner of the present invention (hereinafter sometimes simply referred to as “the toner of the present invention”) will be described in detail.
TmAB <TmAC ≦ TmA Formula (1)

  Here, in the toner of the present invention, the “crystalline resin” refers to a resin having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning calorimetry (DSC). Specifically, a resin whose half-value width of the endothermic peak when measured at a temperature rising rate of 10 ° C./min is within 6 ° C. is defined as “crystalline resin”, and other resins, specifically, half A resin having a value range exceeding 6 ° C. or a resin having no clear endothermic peak is defined as an amorphous polymer (amorphous resin). In addition, even if it does not have a clear endothermic peak in the second temperature raising step, it is “crystalline resin” if it has a clear endothermic peak in the first temperature raising step. As the amorphous polymer used in the present invention, it is preferable to use a resin in which no clear endothermic peak is observed.

In the toner of the present invention, the TmA [° C.], TmAB [° C.], and TmAC [° C.] are measured by a differential scanning calorimeter (manufactured by Max Science Co., Ltd .: DSC3110, thermal analysis system 001, hereinafter “DSC”. It was measured using a thermal analysis apparatus. In the first temperature raising step, the temperature is raised from room temperature to 150 ° C. at a rate of 10 ° C. per minute, held at 150 ° C. for 5 minutes, and then liquefied nitrogen is used to reach 0 ° C. at a rate of 10 ° C. per minute. After lowering the temperature for 5 minutes and holding at 0 ° C., as the second temperature raising step, the temperature was raised again from 0 ° C. to 150 ° C. at a rate of 10 ° C. per minute, and the obtained differential scanning calorimetry curve was analyzed according to JIS K-7121 An endothermic peak was obtained.
The TmAB [° C.] is obtained by mixing the crystalline resin A and the amorphous polymer B with 20 parts by mass of the crystalline resin A and 80 parts by mass of the amorphous polymer B, and then placing the sample on an aluminum dish. , Left at 100 ° C. for 2 hours, slowly cooled at room temperature, and then measured as a sample of a molten sample crushed in a mortar. The TmAC [° C.] After powder mixing the amorphous polymer C with 80 parts by mass of the amorphous polymer C with respect to 20 parts by mass of the crystalline resin A, the sample was placed on an aluminum dish, allowed to stand at 100 ° C. for 2 hours, and slowly cooled at room temperature. The melted sample was crushed with a mortar and measured as a sample.

As the binder resin in the present invention, crystalline resin A and amorphous polymer B are used. When these resins are mixed and used as a binder resin for a toner, it is most important that the resin is in an appropriate compatible state. This is because, in addition to the sharp melt property that the crystalline resin A originally has, the sharp melt and low temperature fixability can be expressed by the plasticizing effect of the compatibilized portion.
In addition, when the resin is appropriately mixed, the dispersibility of the crystalline resin A is improved and the strength of the toner can be ensured.

As an index representing the degree of compatibilization between the crystalline resin A and the amorphous polymer B, it was found that it was most effective to represent the change in the endothermic peak temperature derived from the crystalline resin A in differential scanning calorimetry (DSC). did.
This indicates that the crystalline resin A and the amorphous polymer B are compatibilized so that the crystallinity of the crystalline resin A is lost and the melting point of the crystalline resin is lowered. The endothermic peak temperature derived from the crystalline resin A is also significantly reduced.

  The melting point drop and plasticization of the amorphous polymer due to this compatibilization show excellent sharp melt properties and low temperature fixability, but on the other hand it causes deterioration of heat storage properties such as blocking resistance. By covering the crystalline resin A and the amorphous polymer B with the surface layer mainly composed of the amorphous polymer C having low compatibility with the crystalline resin A different from the amorphous polymer B Both the compatibilized crystalline resin A and amorphous polymer B, and the uncompatibilized crystalline resin A can be suppressed from being exposed to the toner particle surface. This utilizes the relative relationship between the degree of compatibilization between the crystalline resin A and the amorphous polymers B and C, and by positioning the amorphous polymer C, which is difficult to compatibilize with the crystalline resin, in the toner particle surface layer portion, Even in a wet process toner using an agglomeration and coalescence method in which the aggregated particles are coalesced by raising the temperature above the glass transition temperature of the binder resin, the crystalline resin A is exposed to the toner particle surface or the phase of the toner surface layer The melting point of the crystalline resin A and the influence of plasticization of the amorphous polymer B or C due to the melting can be suppressed, thereby maintaining the high-temperature blocking resistance of the toner, and excellent sharp melt properties It became possible to obtain low-temperature fixability. In the present invention, “having amorphous polymer C as a main component” means that the content of amorphous polymer C is 50% by mass or more, and preferably 80% by mass or more.

  In the present invention, the difference obtained by subtracting TmAB [° C.] from TmAC [° C.] is preferably 1 to 20 [° C.], more preferably 5 to 15 [° C.]. When the difference obtained by subtracting TmAB [° C.] from TmAC [° C.] is 1 to 20 [° C.], excellent sharp melt property and low temperature fixability are obtained while maintaining the blocking resistance of the toner at high temperature. The effect that it becomes possible becomes more remarkable.

The toner of the present invention further includes a release agent D, the amorphous polymer B is an amorphous polyester resin B ′, the solubility parameter SP _A of the crystalline resin A, and the amorphous polymer B solubility and the parameter SP _B, and the solubility parameter SP _C of the amorphous polymer C, a solubility parameter SP _D of the releasing agent D, preferably satisfy the relation of the following formula (2). The solubility parameter (hereinafter sometimes referred to as “SP value”) was calculated by the method of Fedors et al. [Polym. Eng. Sci. , Vol14, p147 (1974)].
SP value = (ΣΔei / ΣΔvi) ^1/2
Δei: Evaporation energy of atom or atomic group Δvi: Molar volume of atom or atomic group • SP _D <SP _A <SP _B <SP _C (2)

  When the crystalline resin A and the amorphous polyester resin B ′ are incompatible with each other and have a layer separation structure, the crystalline resin A used as a binder resin can be used to obtain a sharp melt property (low temperature fixability). It is desirable to increase the ratio, but in that case, the strength of the toner itself is extremely reduced, and the external additive is buried by stirring with the carrier in the developing device, or the cleaning member or direct charging, transfer member Occurrence of toner crushing due to image formation or image strength after fixing may be significantly reduced. In addition, when the compatibility of the crystalline resin A and the amorphous polyester resin B ′ is excessively advanced, the crystallinity of the crystalline resin A is lost, the melting point of the crystalline resin is lowered, and the amorphous polyester resin B ′ Although plasticization occurs and exhibits excellent sharp melt properties and low-temperature fixability, if the plasticized amorphous polyester resin B ′ is present on the surface of the toner particles, heat storage properties and chargeability are deteriorated. There is a case.

  In addition, when the crystalline resin A used as the binder resin is a crystalline polyester resin, the wettability with the release agent D generally used is poor, and toner particles are produced using an agglomeration and fusion coalescence method. In this case, the coalescence process by heating proceeds and a release agent (wax) may be exposed on the surface of the toner particles. The exposure of the binder resin and the release agent that are excessively compatible as described above to the toner particle surface adversely affects the heat storage property and charging property, and it is desired to suppress the surface exposure of these materials. .

  Therefore, the amorphous polymer C having a low compatibility with the crystalline resin A and the release agent D is a main component in the core particles containing the release agent D together with the crystalline resin A and the amorphous polyester resin B ′. By coating the surface layer, it becomes possible to suppress the exposure of the release agent D and the compatible crystalline resin A, the amorphous polyester resin B ′, and the crystalline resin A in the crystalline state on the toner particle surface. Excellent thermal storage and chargeability and low-temperature fixability can be achieved at the same time. This utilizes the relative relationship between the affinity of the amorphous polyester resin B ′ and the amorphous polymer D with respect to the crystalline resin A, and this relative relationship is defined as a function of the intermolecular cohesive energy density. And the above expression (3) showing the relative relationship between the SP values of the release agents.

  By covering the surface layer of the toner particle with a surface layer mainly composed of the crystalline resin A and the release agent D and the amorphous polymer C which is difficult to be compatibilized, the crystalline resin A and the release agent on the surface of the toner particle are coated. Even if the agent D is fused and united, due to the difference in compatibility, it can be kept on the side of the amorphous polyester resin B ′ used as the binder resin, and the exposure to the surface can be greatly suppressed.

In addition, regarding the relative relationship between the amorphous polyester resin B ′ (amorphous polymer B) and the SP value of the release agent D, an appropriate compatibility is required, and the relationship of the following formula (3) is satisfied. It is more preferable.
_{· 0.8 <SP B - SP D} <1.8 ··· formula (3)

When the (SP _B -SP _D ) is larger than 1.8, the compatibility between the amorphous polymer B and the release agent D is deteriorated, and the toner is fused and united in the aggregation / fusion uniting method. Desorption of the release agent D from the toner particles may occur. On the other hand, when the (SP _B -SP _D ) is less than 0.8, the crystalline resin A and the amorphous polymer B and the release agent D are compatible, and the release effect is lowered. There is. The (SP _B -SP _D ) is preferably larger than 0.8 and smaller than 1.2.

Further, the SP B of the crystalline resin A and the amorphous polymer B is preferably such that SP _B is larger than SP _A. When SP _B is less than or equal to SP _A , the compatibility of the crystalline resin A and the amorphous polymer B increases, the plasticization of the binder resin increases, and the amorphous polymer located in the surface layer. Since compatibility with C also increases, exposure of the crystalline resin A to the surface layer or plasticization of the amorphous polymer C may progress, which may cause deterioration of the heat storage property of the toner.

  Furthermore, the toner of the present invention has an endothermic peak derived from the crystalline resin A in the temperature range of 50 to 100 ° C. in the first temperature rising process and the release in the differential scanning calorimetry curve obtained by measurement with a differential scanning calorimeter. The sum E of the endothermic amounts of the endothermic peak derived from the agent D is larger than the sum F of the endothermic amounts of the endothermic peak derived from the crystalline resin A and the endothermic peak derived from the release agent D in the second temperature rising process after cooling. It is preferable.

Here, the first temperature raising process corresponds to a thermal history in the fixing step when forming an image, and with the melting of the crystalline resin A and the release agent D, the crystalline resin A and the release agent D, The compatibility with the amorphous polyester resin B ′ (amorphous polymer B) used as the binder resin rapidly advances, the viscoelasticity of the toner rapidly decreases and at the same time is fixed by pressure, and has excellent low-temperature fixability. Can be acquired. Further, the second temperature raising process performed after cooling in the differential scanning calorimeter indicates the thermal characteristics of the toner on the image after fixing.
In the present invention, the total endotherm E of the endothermic peak and the total endotherm F of the endothermic peak are DSC under the same conditions as the measurement of TmA [° C.], TmAB [° C.], and TmAC [° C.]. The measurement is performed, the obtained differential scanning calorimetry curve is analyzed, and is obtained from the endothermic peak and the area surrounded by the baseline in the first temperature rising process and the second temperature rising process after cooling, respectively. .

  In the present invention, the crystalline resin A and the releasing agent D and the amorphous polymer B are compatible with each other in the first temperature raising step, and the crystalline resin portion is also compatible in the subsequent cooling step. In the second temperature raising step, the total endothermic amount of the endothermic peaks derived from the crystalline resin A and the release agent D is small. Thereby, in the fixing state, the relatively brittle crystalline resin A and the release agent D are reduced, so that the image strength such as the bending strength of the image fixed on the paper or the like is improved, and the non-binding resin in the binder resin is improved. The irregular reflection of light and the like at the interface between the crystalline polyester resin B ′ and the crystalline resin is suppressed, and the light transmittance of the image is improved.

  As described above, by defining the relative relationship between the SP values and the thermal characteristics measured by the differential scanning calorimeter of the toner, the temperature is raised above the glass transition temperature of the binder resin, and the aggregated particles are coalesced. In wet-process toner using agglomeration and coalescence method, the effects of the crystalline resin exposure to the toner particle surface or the melting point of the crystalline resin due to the compatibility of the toner surface layer and the plasticization of the amorphous polymer are suppressed. As a result, it is possible to obtain excellent sharp melt property, low temperature fixing property, and excellent image strength and image quality while maintaining the blocking resistance of the toner at high temperature.

The toner of the present invention includes a crystalline resin A and an amorphous polymer B, and the surface is coated with a surface layer mainly composed of an amorphous polymer C different from the amorphous polymer B. ) Is not particularly limited, but may include other components such as a release agent D. The method for producing the toner of the present invention is not particularly limited, but it is preferable to use a wet method as described later.
Hereinafter, the components of the toner of the present invention will be described in detail.

  The toner of the present invention preferably contains 5 to 50% of the crystalline resin A. When the content of the crystalline resin exceeds 50%, good fixing characteristics can be obtained, but the phase separation structure in the fixed image becomes non-uniform, and the strength of the fixed image, particularly the scratch strength, is reduced and scratched. It may be easier. On the other hand, if the content of the crystalline resin is less than 5%, the sharp melt property derived from the crystalline resin A cannot be obtained, and the amorphous polymer B is simply plasticized, and good low-temperature fixability. In some cases, the toner blocking resistance and the image storage stability cannot be maintained while securing the toner.

The crystalline resin A is not particularly limited as long as it is a resin having crystallinity, and specifically includes a crystalline polyester resin and a crystalline vinyl resin. From the viewpoint of chargeability and adjustment of the melting point within a preferred range, a crystalline polyester is preferred. An aliphatic crystalline polyester resin having an appropriate melting point is more preferable.
The crystalline polyester resin and all other polyester resins used in the toner of the present invention are synthesized from a polyvalent carboxylic acid component and a polyhydric alcohol component. In the present invention, a commercially available product may be used as the polyester resin, or an appropriately synthesized product may be used. Hereinafter, the crystalline polyester resin preferably used as the crystalline resin A will be described.

Examples of the polyvalent 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, Aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconine Aromatic dicarboxylic acids such as dibasic acids such as acids, and the like, and anhydrides and lower alkyl esters thereof are also included, but not limited thereto.
Examples of trivalent or higher carboxylic acids 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.

  Furthermore, the polyvalent carboxylic acid component preferably contains a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above. The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. In addition, when the entire crystalline polyester resin is emulsified or suspended in water to produce fine particles, if a sulfonic acid group is present, it can be emulsified or suspended without using a surfactant as described later. is there.

  Examples of the dicarboxylic acid having a sulfonic acid 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. The divalent or higher carboxylic acid component having a sulfonic acid group is preferably contained in an amount of 0 to 20 mol%, and preferably 0.5 to 10 mol%, based on all polyvalent carboxylic acid components constituting the polyester. It is more preferable. When the content of the divalent or higher carboxylic acid component is less than 0.5 mol%, the stability over time of the emulsified particles may deteriorate. If it exceeds 10 mol%, not only the crystallinity of the polyester resin will be lowered, but also the process of fusing the particles after agglomeration will be adversely affected and it may be difficult to adjust the toner diameter.

  Furthermore, it is more preferable to contain a dicarboxylic acid component having a double bond in addition to the aforementioned aliphatic dicarboxylic acid and aromatic dicarboxylic acid. 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, 3-octenedioic acid, and their lower esters and acid anhydrides. Among these, fumaric acid and maleic acid are preferable in terms of cost.

  The polyhydric alcohol component is preferably an aliphatic diol, and more preferably a linear aliphatic diol having a main chain portion having 7 to 20 carbon atoms. 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. Further, when the number of carbon atoms is less than 7, when polycondensation with an aromatic dicarboxylic acid, the melting point becomes high and fixing at low temperature may be difficult. On the other hand, when the number of carbon atoms exceeds 20, it may be difficult to obtain practical materials. The aliphatic diol preferably has 7 to 14 carbon atoms.

Specific examples of the aliphatic diol suitably used for the synthesis of the crystalline polyester used in the toner of the present invention include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5. -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12- Examples include, but are not limited to, dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, and the like. Among these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type and may use 2 or more types together.

  Among the polyhydric alcohol components, the content of the aliphatic diol component is preferably 80 mol% or more, and more preferably 90% or more. If the content of the aliphatic diol component is less than 80 mol%, the crystallinity of the polyester resin may be lowered. If necessary, monovalent acids such as acetic acid and benzoic acid and monovalent alcohols such as cyclohexanol benzyl alcohol can be used for the purpose of adjusting the acid value and hydroxyl value.

The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Depending on the type of monomer, it is manufactured separately.
The production of the crystalline polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction is carried out while reducing the pressure in the reaction system as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible with the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. When a monomer having poor compatibility exists in the copolymerization reaction, the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

  The crystalline polyester resin fine particle dispersion can be prepared by adjusting the acid value of the resin and emulsifying and dispersing the resin using an ionic surfactant.

  Catalysts that can be used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compounds: Phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like, and specific examples include the following compounds. For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisoproxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthenic acid Zirconium, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Sufaito, tris (2, 4-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

As melting | fusing point of crystalline resin A, Preferably it is 50-100 degreeC, More preferably, it is 60-80 degreeC. If the melting point of the crystalline resin A is lower than 50 ° C., toner storage stability and toner image storage stability after fixing may become a problem. On the other hand, if the melting point of the crystalline resin A is higher than 100 ° C., sufficient low-temperature fixing may not be obtained as compared with conventional toners.
A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  On the other hand, the crystalline vinyl resin includes amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, (meth) acrylic. Decyl acid, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, (meth) acrylic acid Examples thereof include vinyl resins using long-chain alkyl such as behenyl and alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means to include both “acryl” and “methacryl”.

  As the amorphous polymer B, a known resin material can be used, but an amorphous polyester resin B ′ is particularly preferable. The non-crystalline polyester resin B ′ preferably used in the present invention is obtained mainly by condensation polymerization of polyvalent carboxylic acids and polyhydric alcohols. When the amorphous polyester resin B ′ is used as the amorphous polymer B, a resin particle dispersion is easily prepared by emulsifying and dispersing the resin by adjusting the acid value or using an ionic surfactant. This is advantageous in that it can.

  Examples of the polyvalent carboxylic acid in the non-crystalline polyester resin B ′ include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid; Aliphatic carboxylic acids such as acid, fumaric acid, succinic acid, alkenyl succinic anhydride, and adipic acid; cycloaliphatic carboxylic acids such as cyclohexanedicarboxylic acid, and one or more of these polyvalent carboxylic acids are used. be able to. Among these polycarboxylic acids, aromatic carboxylic acids are preferably used, and trivalent or higher carboxylic acids (trimellitic acid) together with dicarboxylic acids to form a crosslinked structure or a branched structure in order to ensure good fixing properties. And acid anhydrides thereof) are preferably used in combination.

  Examples of the polyhydric alcohol in the non-crystalline polyester resin B ′ include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentylglycol, glycerin, etc .; cyclohexanediol And alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol A; aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. One or more of these polyhydric alcohols can be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and among these, aromatic diols are more preferable. In order to secure better fixability, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol) may be used in combination with the diol in order to form a crosslinked structure or a branched structure.

  In addition, monocarboxylic acid and / or monoalcohol is further added to the polyester resin obtained by polycondensation of polycarboxylic acid and polyhydric alcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal. The acid value of the polyester resin may be adjusted. Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, etc., and examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, trifluoroethanol, Examples include trichloroethanol, hexafluoroisopropanol, and phenol.

  The non-crystalline polyester resin B ′ can be produced by subjecting the polyhydric alcohol and polyvalent carboxylic acid to a condensation reaction according to a conventional method. For example, the polyhydric alcohol and polyhydric carboxylic acid, if necessary, a catalyst is added, blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Can be manufactured.

  Examples of the catalyst used for the synthesis of the amorphous polyester resin B ′ include esterification catalysts such as organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. The amount of such a catalyst added is preferably 0.01 to 1.00% by mass relative to the total amount of raw materials.

  The amorphous polymer B has a weight average molecular weight (Mw) of 5,000 to 1,000,000, preferably 7,000 to 500,000 by molecular weight measurement by gel permeation chromatography (GPC) method of tetrahydrofuran (THF) soluble content. More preferably. The number average molecular weight (Mn) is preferably from 2000 to 10,000, and the molecular weight distribution Mw / Mn is preferably from 1.5 to 100, more preferably from 2 to 60. When the amorphous polymer B has a weight average molecular weight of less than 5,000 or a number average molecular weight of less than 2,000, it is effective for low-temperature fixability but deteriorates the hot offset resistance. In some cases, the storage stability such as toner blocking due to the decrease in toner may be adversely affected. On the other hand, when the weight average molecular weight of the amorphous polymer B exceeds 1,000,000 or the number average molecular weight exceeds 10,000, the hot offset resistance can be sufficiently provided, but the low-temperature fixability is lowered and the crystals present in the toner are also reduced. This may hinder the storability of the protective polyester phase and thus adversely affect document preservation. Therefore, by setting the weight average molecular weight to 5,000 to 1,000,000 or the number average molecular weight to 2,000 to 10,000, it becomes easy to achieve both low-temperature fixability, hot offset resistance, and document storage stability.

  In the present invention, the molecular weight of the resin used is determined by measuring THF solubles using a TOSOH column / TSKgel Super HM-M (15 cm) using a TOSOH GPC / HLC-8120 and a monodisperse polystyrene. The molecular weight was calculated using a molecular weight calibration curve prepared with a standard sample.

  Further, the acid value of the polyester resin (mg number of KOH necessary for neutralizing 1 g of the resin) makes it easy to obtain the molecular weight distribution as described above, and it is easy to ensure the granulation property of the toner particles by the emulsion dispersion method. In addition, the environmental stability (stability of chargeability when the temperature and humidity change) of the obtained toner is easy to keep good, and the like, it is preferably 1 to 30 mg KOH / g. The acid value of the polyester resin can be adjusted by controlling the carboxyl group at the terminal of the polyester according to the blending ratio of the raw polyhydric carboxylic acid and polyhydric alcohol and the reaction rate. Or what has a carboxyl group in the principal chain of polyester is obtained by using trimellitic anhydride as a polyvalent carboxylic acid component.

  As the amorphous polymer C, a known amorphous polymer can be used, and a styrene acrylic resin can also be used. Examples of monomers that can be used in this case include styrenes such as styrene, parachlorostyrene, and α-methylstyrene: methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and lauryl acrylate. And esters having vinyl groups such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and the like: Vinyl nitriles such as acrylonitrile and methacrylonitrile: Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether: Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone: Polyolefins such as ethylene, propylene and butadiene: Single amount And a copolymer obtained by combining two or more of these, or a mixture thereof. Furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl It is also possible to use a condensation resin, a mixture of these with the vinyl resin, or a graft polymer obtained when a vinyl monomer is polymerized in the presence of these resins. The amorphous polymer C is preferably an amorphous polyester resin.

  When the amorphous polymer C is produced using a vinyl monomer, a resin fine particle dispersion can be produced by carrying out emulsion polymerization using an ionic surfactant or the like. In the case of a resin, if it is oily and dissolves in a solvent having a relatively low solubility in water, the resin is dissolved in those solvents and dissolved in water with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte. The resin fine particle dispersion can be prepared by dispersing the fine particles in the solution and then heating or reducing the pressure to evaporate the solvent.

  When the amorphous polymer C is an amorphous polyester, the resin particle dispersion can be easily prepared by adjusting the acid value of the resin and emulsifying and dispersing in water with a dispersing machine such as a homogenizer using a neutralized amine. It is advantageous in that it can be prepared.

The particle size of the resin fine particle dispersion of the amorphous polymer C thus obtained can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
The glass transition temperature of the amorphous polymer C used in the present invention is preferably 35 to 100 ° C., and more preferably 50 to 80 ° C. from the viewpoint of the balance between storage stability and toner fixing property. preferable. If the glass transition temperature is less than 35 ° C., the toner may be blocked during storage or in a developing machine (a phenomenon in which toner particles are aggregated into a lump). On the other hand, if the glass transition temperature exceeds 100 ° C., the toner fixing temperature may increase.

Moreover, it is preferable that the softening point of the amorphous polymer C is 80-130 degreeC, More preferably, it is 90-120 degreeC. If the amorphous polymer C has a softening point of less than 80 ° C., the toner and the image stability of the toner after fixing and storage may deteriorate. On the other hand, when the softening point exceeds 130 ° C., the low-temperature fixability may be deteriorated.
In the present invention, the softening point of the amorphous polymer C is measured using a flow tester (manufactured by Shimadzu Corp .: CFT-500C), preheating: 300 seconds at 80 ° C., plunger pressure: 0.980665 MPa, die size: 1 mmφ × 1 mm, temperature increase rate: An intermediate temperature between the melting start temperature and the melting end temperature under the condition of 3.0 ° C./min.

  The release agent D is not particularly limited as long as it is a known release agent. For example, natural wax such as carnauba wax, rice wax, candelilla wax, low molecular weight polypropylene, low molecular weight polyethylene, sasol wax, Examples include, but are not limited to, synthesis of microcrystalline wax, Fischer-Tropsch wax, paraffin wax, montan wax, and the like, or ester-based waxes such as mineral / petroleum wax, 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 D is preferably 50 ° C. or higher, and 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.

  The content of the release agent D in the toner is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the binder resin. preferable. When the content of the release agent D is less than 1 part by mass, there is no effect of addition of the release agent, and hot offset at a high temperature may be caused. On the other hand, if it exceeds 30 parts by mass, the chargeability is adversely affected, and the mechanical strength of the toner is reduced. Therefore, the toner is easily destroyed by stress in the developing machine, and may cause carrier contamination. Further, when used as a color toner, a domain tends to remain in a fixed image, which may cause a problem that OHP transparency is deteriorated.

  The colorant used in the toner of the present invention is not particularly limited as long as it is a known colorant, and examples thereof include carbon black such as furnace black, channel black, acetylene black, and thermal black, bengara, bitumen, and titanium oxide. 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, Examples include condensed polycyclic pigments such as dioxazine violet, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, Lozon Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Risor 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 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. Examples thereof include various pigments such as CI Pigment Blue 15: 3, and these can be used alone or in combination of two or more.

  In the toner of the present invention, the content of the colorant is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. Alternatively, a surface-treated colorant may be used if necessary. It is also effective to use a pigment dispersant. By appropriately selecting the type of the colorant, yellow toner, magenta toner, cyan toner, black toner and the like can be obtained.

Various components such as an internal additive, a charge control agent, inorganic powder (inorganic fine particles), and organic fine particles can be further added to the toner of the present invention 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 and the like are listed in detail below. And all inorganic fine particles used as external additives on the toner surface.

Further, examples of the inorganic fine particles and organic fine particles externally added to the toner surface of the present invention include the following.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride. , Bengala, 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.

The inorganic fine particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic fine particles is preferably 1 to 200 nm, and the addition amount is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the toner.
The organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specifically include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

The viscoelastic properties of the toner of the present invention preferably further satisfy the following conditions.
The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. is preferably 1 × 10 ⁷ Pa or more, and the loss elastic modulus GN (90) at 90 ° C. is 1.0 × 10 ⁵ Pa or less. preferable. When the storage elastic modulus GL (30) is less than 1 × 10 ⁷ Pa, when used as a toner in a two-component developer, when mixed with a carrier in a developing machine, toner particles are applied by pressure or shear force received from the carrier. When the toner is deformed and stable charge development characteristics cannot be maintained, or when the toner on the electrostatic latent image carrier is cleaned, it is deformed by the shearing force received from the cleaning blade, resulting in poor cleaning. There is. On the other hand, when the storage elastic modulus GL (30) is 1 × 10 ⁷ Pa or more, the characteristics are stable even when used with a high-speed machine, and the strength of the image after fixing can be further increased. On the other hand, when the loss elastic modulus GL (90) exceeds 1.0 × 10 ⁵ Pa, the low-temperature fixability may be deteriorated.

In the present invention, the storage elastic modulus GL (30) is more preferably 1 × 10 ⁸ Pa or more.
The loss elastic modulus GN (90) is more preferably 5 × 10 ^{3 to} 1.0 × 10 ⁵ Pa, and further preferably 1 × 10 ^{4 to} 5.0 × 10 ⁴ Pa.

  The toner of the present invention has, for example, a particle size range (channel) obtained by dividing the particle size distribution measured using a measuring instrument such as Coulter Counter TAII (manufactured by Beckman-Coulter) or Multisizer II (manufactured by Beckman-Coulter). On the other hand, a cumulative distribution is drawn from the small diameter side to each of the volume and the number, the particle diameter that becomes 16% cumulative is the volume D16%, the particle diameter that becomes 50% cumulative is the volume D50%, and the particle diameter that becomes 84% cumulative is the volume D84. %, The volume average particle size distribution index (GSDv) calculated from D84% / D16% is preferably 1.15 to 1.30, and preferably 1.15 to 1.25. More preferred.

  The charge amount of the toner of the present invention is an absolute value, preferably 20 to 55 μC / g, and more preferably 25 to 45 μC / g. If the charge amount of the toner of the present invention is less than 20 μC / g, background stains (fogging) may occur easily, and if it exceeds 55 μC / g, the image density may decrease easily.

  The shape factor SF1 of the toner of the present invention is preferably 120 ≦ SF1 ≦ 130 from the viewpoint of image formability. The shape factor SF1 of the present invention can be calculated by the average value of the shape factor (the square of the absolute maximum length / projection area) × (100π / 4) (π is the circumference), for example, calculated by the following method Is done. That is, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, calculated from the square of the absolute maximum length ML of 100 toners and the projection area A, and the shape factor of each toner is calculated. It is obtained by obtaining SF1 from the average value.

  By satisfying the characteristics of the respective toners described above, low-temperature fixing is possible, and even in low-speed to high-speed processes, there is little variation in adhesion of a fixed image to a fixing sheet in oil-less fixing and excellent blocking properties. An electrostatic charge developing toner can be obtained.

-Toner production method-
The toner of the present invention generates toner particles in an acidic or alkaline aqueous medium such as agglomeration and coalescence method, suspension polymerization method, solution suspension granulation method, solution suspension method, and solution emulsion aggregation method. However, it is particularly preferable to be produced by an agglomeration coalescence method.
The aggregation coalescence method suppresses the disruption of the ion balance of the aggregation system and makes it easy to control the aggregation rate.In the suspension polymerization method, it suppresses the occurrence of polymerization inhibition, and particularly makes it easy to control the particle diameter. In the dissolution suspension granulation method and the dissolution emulsification aggregation method, it is possible to stabilize particles during granulation and emulsification.

  When the aggregation coalescence method is used, the method for producing the toner of the present invention includes at least the crystalline resin A fine particle dispersion in which the crystalline resin A fine particles are dispersed, and the amorphous polymer B in which the amorphous polymer B fine particles are dispersed. Crystalline properties when a mixed dispersion is prepared by mixing a fine particle dispersion, a polymer of one or more metal salts containing polyaluminum chloride is added thereto, and the mixed dispersion is measured with a differential scanning calorimeter. After forming the aggregated particles at a temperature lower than the endothermic peak temperature of the resin A fine particles, an aggregated fine particle dispersion producing step for producing an aggregated fine particle dispersion obtained by agglomerating and growing the aggregated particles; By adding and mixing an amorphous polymer C fine particle dispersion in which the amorphous polymer C fine particles are dispersed, an adhesion step of attaching the amorphous polymer C fine particles to the surface of the aggregated fine particles, and an aggregation after the adhesion step By the pH of the particle dispersion with a basic, the growth of the aggregated particles is stopped, characterized by having a the steps coalescence to coalescence by heating it.

In the aggregated fine particle dispersion manufacturing step, the polymer of at least one metal salt added when mixing each dispersion is a polymer of a tetravalent aluminum salt, or the polymer of the metal salt is 4 It is preferable that it is a mixture of a valent aluminum salt polymer and a trivalent aluminum salt polymer. Specifically, these polymers include inorganic metal salts such as calcium nitrate, or inorganic metals such as polyaluminum chloride. Examples thereof include a salt polymer. In the present invention, the polymer of the metal salt is preferably polyaluminum chloride.
The metal salt polymer is preferably added so that the concentration in the aggregated fine particle dispersion is 0.11 to 0.25% by mass.

In the production step of the aggregated fine particle dispersion, when the colorant and the release agent D are contained, first, the crystalline resin A fine particle dispersion, the amorphous polymer B fine particle dispersion, the colorant fine particle dispersion, and the release agent D are used. Prepare a particle dispersion.
The crystalline resin A fine particle dispersion is heated by a known phase inversion emulsification or a melting point or higher and emulsified by mechanical shearing force. At this time, an ionic surfactant may be added or the emulsion may be stabilized by self-neutralization using a neutralized amine.

  The amorphous polymer B fine particle dispersion is preferably carried out in the same manner as in the production of the crystalline resin A fine particle dispersion. However, when the amorphous polymer B is capable of emulsion polymerization such as a styrene acrylic resin. It is also preferable to adjust the amorphous polymer B fine particles prepared by emulsion polymerization or the like by dispersing them in a solvent using an ionic surfactant.

  The colorant particle dispersion uses an ionic surfactant opposite in polarity to the ionic surfactant used in the preparation of the resin fine particle dispersion, and the colorant particles of a desired color such as blue, red, and yellow are used as a solvent. It is preferable to adjust by dispersing in.

  The release agent D particle dispersion is prepared by adding and dispersing release agent D in water together with an ionic surfactant, a polymer electrolyte such as a polymer acid or a polymer base, heating the mixture to a temperature higher than the melting point and strong shearing. It is adjusted by making fine particles with a homogenizer or pressure discharge type disperser.

  Next, a mixed dispersion is prepared by mixing the crystalline resin A fine particle dispersion, the amorphous polymer B fine particle dispersion, the colorant particle dispersion, and the release agent D fine particle dispersion. A temperature lower than the endothermic peak temperature of the crystalline resin A fine particles when the mixed dispersion is measured with a differential scanning calorimeter (preferably 40 to 60). Then, the aggregated particles are aggregated and grown to prepare an aggregated fine particle dispersion in which aggregated particles (core aggregated particles) having a diameter substantially close to a desired toner diameter are dispersed.

  In the adhering step, an amorphous polymer C fine particle dispersion in which amorphous polymer C fine particles are dispersed is added to and mixed with the aggregated fine particle dispersion, thereby forming an amorphous high particle on the surface of the aggregated fine particles (core aggregated particles). By attaching molecular C fine particles and forming a surface layer (shell layer) having a desired thickness, aggregated particles (core / shell aggregated particles) having a core / shell structure in which a shell layer is formed on the surface of the core aggregated particles are obtained.

  The particle diameters of the crystalline resin fine particles A, the amorphous polymer B fine particles, the amorphous polymer fine particles C, the colorant fine particles, and the release agent D fine particles used in the production process of the aggregated fine particle dispersion are the toner diameter and In order to make it easy to adjust the particle size distribution to a desired value, it is preferably 1 μm or less, and more preferably in the range of 20 to 300 nm.

  In the aggregated fine particle dispersion manufacturing process, two polar ionic surfactants (dispersants) contained in the crystalline resin A fine particle dispersion, the amorphous polymer B fine particle dispersion, and the colorant fine particle dispersion are used. The amount balance can be shifted in advance. For example, an inorganic metal salt such as calcium nitrate or a polymer of an inorganic metal salt such as polyaluminum chloride is ionically neutralized and heated below the glass transition temperature of the first resin fine particles to agglomerate the core. Particles can be made.

In such a case, in the adhering step, the resin fine particle dispersion treated with the dispersant having the polarity and the amount so as to compensate for the balance between the two polar dispersants is put into the solution containing the core aggregated particles. The core / shell aggregated particles can be prepared by adding and slightly heating the amorphous polymer C fine particles used in the adhesion step slightly below the glass transition temperature if necessary.
The agglomerated fine particle dispersion manufacturing process and the adhering process may be repeated in a plurality of stages.

  In the fusion / unification step, the agglomerated fine particle dispersion (core / shell agglomerated particle dispersion) obtained through the adhering step has a basic pH (preferably pH 9 to 10) so that the agglomerated fine particles are dispersed. Further, in the dispersion, the melting point of the crystalline resin A contained in the core / shell aggregated particles, and the glass transition temperature of the mixture of the amorphous polymer B and C fine particles (the type of the resin is In the case of two or more types, the toner is obtained by fusing and coalescing by heating above the glass transition temperature of the resin having the highest glass point transition temperature) and cooling (preferably up to 40 ° C. or less).

  Furthermore, a desired toner is obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of charging properties. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. On the other hand, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
-Preparation of crystalline polyester resin dispersion (A)-
After putting 98 parts of dimethyl sebacate, 2 moles of sodium dimethyl-5-sulfonate and 100 moles of ethylene glycol into a heat-dried three-necked flask, 0.3 parts by weight of dibutyltin oxide as a catalyst per 100 parts by weight in total. The air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (A) was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (A) was 9700 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (A) was measured using a differential scanning calorimeter (DSC) by the above-described measuring method, it showed a clear endothermic peak, and the endothermic peak temperature was 76.1. ° C.

-Crystalline polyester resin (A) 90 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 1.8 parts by mass-Ion-exchanged water 210 parts by mass Next, the above composition was heated to 100 ° C, After sufficiently dispersing with IKA Ultra Turrax T50, dispersion treatment is performed with a pressure discharge type gorin homogenizer for 1 hour, a crystalline polyester resin dispersion (A having a center diameter of 200 nm and a solid content in 100 parts by mass of 30 parts by mass (A )

-Preparation of crystalline polyester resin dispersion (B)-
After putting 98 parts of dimethyl sebacate, 2 moles of sodium dimethyl-5-sulfonate and 100 moles of ethylene glycol into a heat-dried three-necked flask, 0.3 parts by weight of dibutyltin oxide as a catalyst per 100 parts by weight in total. The air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and the mixture was stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was cooled with air, the reaction was stopped, and a crystalline polyester resin (B) was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (B) was 30000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (B) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 66 ° C. there were.

-Crystalline polyester resin (B) 90 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 1.8 parts by mass-210 parts by mass of ion-exchanged water Then, the composition is heated to 100 ° C, After sufficiently dispersing with IKA Ultra Turrax T50, dispersion treatment is performed with a pressure discharge type gorin homogenizer for 1 hour, and a crystalline polyester resin dispersion (B) having a central diameter of 130 nm and a solid content in 100 parts by mass of 30 parts by mass. )

-Preparation of crystalline polyester resin dispersion (C)-
In a heat-dried three-necked flask, 90.5 mol of 1,10-dodecanedioic acid, 2 mol of dimethyl-5-sulfonic acid sodium salt, 7.5 mol of 5-t-butylisophthalic acid, 100 mol of 1,9-nonanediol, After adding 0.3 parts by mass of dibutyltin oxide as a catalyst per 100 parts by mass in total, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization and stirred at 180 ° C. for 5 hours with mechanical stirring. Reflux was performed. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 4 hours. When it became viscous, it was cooled with air, the reaction was stopped, and a crystalline polyester resin (C) was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (C) was 28000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (C) was measured using a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 72 ° C. there were.

-Crystalline polyester resin (C) 90 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 1.8 parts by mass-Ion-exchanged water 210 parts by mass Next, the above composition was heated to 100 ° C, After sufficiently dispersing with IKA Ultra Turrax T50, dispersion treatment is performed with a pressure discharge type gorin homogenizer for 1 hour, and a crystalline polyester resin dispersion (C) having a central diameter of 300 nm and a solid content in 100 parts by mass of 30 parts by mass. )

-Preparation of crystalline polyester resin dispersion (D)-
In a heat-dried three-necked flask, 95 mol of dimethyl terephthalate, 5 mol of dimethyl-5-sodium phthalate, 100 mol of 1,9-nonanediol, and 0.3 parts by mass of dibutyltin oxide as a catalyst per 100 parts by mass in total. Then, the air in the container was brought into an inert atmosphere with nitrogen gas by depressurization, and stirred and refluxed at 180 ° C. for 5 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When the mixture became viscous, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (D) was synthesized. The weight average molecular weight (Mw) of the obtained crystalline polyester resin (D) was 4000 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography. Further, when the melting point (Tm) of the crystalline polyester resin (D) was measured by a differential scanning calorimeter (DSC) by the above-described measurement method, it showed a clear endothermic peak, and the endothermic peak temperature was 94 ° C. there were.

-Crystalline polyester resin (D) 90 parts by mass-Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5.0 parts by mass-Ion-exchanged water 210 parts by mass Next, the above composition was heated to 100 ° C, After sufficiently dispersing with IKA Ultra Turrax T50, dispersion treatment is performed for 1 hour with a pressure discharge type gorin homogenizer, and a crystalline polyester resin dispersion (D) having a center diameter of 320 nm and a solid content in 100 parts by mass of 30 parts by mass. )

-Preparation of Amorphous Polyester Resin (Amorphous Polymer) Dispersion (e)-
30 mol of terephthalic acid, 70 mol of fumaric acid, 20 mol of bisphenol A ethylene oxide 2 mol adduct, and 80 mol of bisphenol A propylene oxide adduct are placed in a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column. After charging, the temperature was raised to 190 ° C. over 1 hour, and after confirming that the inside of the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to increase the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 3 hours. An amorphous polyester resin (e) of 9700 was obtained.

Subsequently, the obtained amorphous polyester resin (e) was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (e) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). A Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ^2. A dispersed amorphous polyester resin dispersion (e) dispersion was obtained.

-Preparation of amorphous polyester resin (amorphous polymer) dispersion (f)-
100 mol of terephthalic acid, 90 mol of bisphenol A ethylene oxide 2 mol adduct, and 10 mol of cyclohexanedimethanol are charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column, and one hour is required. The temperature was raised to 190 ° C., and after confirming that the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 3 hours. The acid value was 9.0 mg / KOH, the weight average molecular weight. An amorphous polyester resin (f) of 9000 was obtained.

Subsequently, the obtained amorphous polymer resin (f) was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (e) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). A Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ^2. A dispersed amorphous polyester resin dispersion liquid dispersion (f) was obtained.

-Preparation of amorphous polyester resin (amorphous polymer) dispersion (g)-
80 mol% terephthalic acid, 20 mol% isophthalic acid, 90 mol% bisphenol A propylene oxide 2-mol adduct, 10 mol% ethylene glycol were placed in a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification column. Was added to 190 ° C. over 1 hour, and after confirming that the inside of the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, it took 6 hours from the same temperature to increase the temperature to 240 ° C., and continued the dehydration condensation reaction at 240 ° C. for another 5 hours. An amorphous polyester resin (g) of 8500 was obtained.

Subsequently, the obtained amorphous polymer resin (g) was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (e) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). A Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ^2. A dispersed amorphous polyester resin dispersion (g) was obtained.

-Preparation of amorphous polymer dispersion (h)-
80 mol of terephthalic acid, 20 mol of isophthalic acid, 90 mol of bisphenol A propylene oxide 2 mol adduct, and 10 mol of ethylene glycol were charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectification column for 1 hour. After confirming that the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was increased to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for further 5 hours. An amorphous polyester resin (h) of 30000 was obtained.

Subsequently, the obtained amorphous polymer resin (h) was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. Separately prepared aqueous medium tank is filled with 0.37 wt% diluted ammonia water diluted with ion-exchanged water with reagent-exchanged water, and heated at 120 ° C with a heat exchanger at a rate of 0.1 liter per minute. The amorphous polyester resin (e) melt was transferred to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.). The Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ^{2. From} an amorphous polyester resin (h) having an average particle size of 0.13 μm and a solid content in 100 parts by mass of 30 parts by mass An amorphous polyester resin dispersion (h) was obtained.

-Preparation of Amorphous Polyester Resin (Amorphous Polymer) Dispersion (i)-
370 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 4 parts by mass of acrylic acid, 24 parts by mass of dodecanethiol, and 4 parts by mass of carbon tetrabromide were mixed and dissolved in a nonionic surfactant (Sanyo Chemical ( Co., Ltd .: Nonipol 400) 6 parts by mass and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts by mass were dissolved in 560 parts by mass of ion-exchanged water and dispersed in a flask. While emulsifying and slowly mixing for 10 minutes, 50 parts by mass of ion-exchanged water in which 4 parts by mass of ammonium persulfate was dissolved was added thereto, followed by nitrogen substitution. The mixture was heated in an oil bath until it reached 0 ° C., and emulsion polymerization was continued for 5 hours. Thus, an amorphous polymer dispersion (i) obtained by dispersing resin particles having an average particle diameter of 180 nm, a glass transition point of 55 ° C., and a weight average molecular weight (Mw) of 15000 (the solid content in 100 parts by mass is 30 parts by mass) was prepared.

-Preparation of colorant dispersion-
・ Cyan pigment (copper phthalocyanine B15: 3: manufactured by Dainichi Seika) 45 parts by mass ・ Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by mass ・ Ion-exchanged water 200 parts by mass IKA Ultra Tarrax) for 10 minutes to obtain a colorant dispersion having a central particle size of 168 nm and a solid content in 100 parts by mass of 23.0 parts by mass.

-Preparation of release agent dispersion (j)-
Carnauba wax (melting point: 81 ° C.) 45 parts by mass Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by mass 200 parts by mass of ion-exchanged water Was sufficiently dispersed in a pressure discharge type gorin homogenizer to obtain a release agent dispersion (j) having a center diameter of 200 nm and a solid content in 100 parts by mass of 20% by mass.

-Preparation of release agent dispersion (k)-
・ Pentaerythritol behenate ester wax (melting point: 84.5 ° C.) 5 parts by mass • Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by mass • Ion-exchanged water 200 parts by mass The above is heated to 95 ° C. The dispersion was sufficiently dispersed with IKA Ultra Turrax T50, and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion (k) having a center diameter of 220 nm and a solid content in 100 parts by mass of 20%. .

-Preparation of release agent dispersion (l)-
-Paraffin wax HNP-9 (Nippon Seiki, melting point 75 ° C) 45 parts by mass-Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by mass-Ion-exchanged water 200 parts by mass After sufficiently dispersing with IKA Ultra Turrax T50, it was dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion (l) having a center diameter of 190 nm and a solid content in 100 parts by mass of 20%.

  The endothermic peak temperature TmA of the obtained crystalline resins (A) to (D) and the endothermic peak when mixed in combination with the amorphous polymer dispersions (e) to (i) (TmAB in the present invention or This corresponds to TmAC and was measured by the TmAB and TmAC measurement methods described above.

Example 1
-Production of toner base particles (1)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by mass Crystalline resin fine particle dispersion (B) 66.7 parts by mass Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.0 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.5 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.9 μm, and the particle size distribution coefficient GSD was 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.
Further, the viscoelasticity of the toner base particles (1) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 3.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 1.2 × 10 ⁴ Pa. The measurement was performed by setting the toner to be measured on the sample holder, the temperature rising rate: 1 ° C./min, the frequency: 1 Hz, the distortion: 20% or less, and the detected torque within the range of the measurement compensation value. In addition, the sample holder was properly used for 8 mm and 20 mm as needed.

-Preparation of external additive toner (1)-
Next, an external toner was prepared as follows.
100 parts by mass of the toner base particles (1), 1.0 part by mass of rutile-type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size) 40 nm, silicone oil treatment) 2.0 parts by mass, higher alcohol pulverized product (volume average particle size 8 μm) 0.5 part by mass was added and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (1).

(Example 2)
-Production of toner base particles (2)-
Amorphous polymer resin fine particle dispersion (g) 183.3 parts by weight Crystalline resin fine particle dispersion (B) 33.3 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.2 with an aqueous 0.5 mol / l sodium hydroxide solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.3 and the electric conductivity was 7.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.0 μm, and the particle size distribution coefficient GSD was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 135.
The viscoelasticity of the toner base particles (2) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 7.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 8.0 × 10 ⁴ Pa.

-Preparation of external additive toner (2)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (2), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (2).

(Example 3)
-Preparation of toner base particles (3)-.
Amorphous polymer resin fine particle dispersion (g) 83.3 parts by weight Crystalline resin fine particle dispersion (B) 133.3 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was further repeated 5 times, and when the pH of the filtrate became 7.4 and the electric conductivity was 7.2 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.1 μm, and the particle size distribution coefficient GSD was 1.26. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 129.
The viscoelasticity of the toner base particles (3) was measured using a rotating plate rheometer (RDA 2RHIOS System Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). The storage elastic modulus GL (30) at 30 ° C. at an angular frequency of 1 Hz was 7.2 × 10 ⁷ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 1.5 × 10 ⁴ Pa.

-Preparation of external additive toner (3)-
Next, an external toner was prepared. Toner base particle (3) 100 parts by mass, rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment) 1.0 part by mass, silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (3).

Example 4
-Production of toner base particles (4)-
Amorphous polymer resin fine particle dispersion (g) 183.3 parts by weight Crystalline resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 33.3 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.3 and the electric conductivity was 9.5 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.2 μm, and the particle size distribution coefficient GSD was 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 126.
Further, the viscoelasticity of the toner base particles (4) was measured using a rotating plate type rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 1.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 3.0 × 10 ⁴ Pa.

-Preparation of external additive toner (4)-
Next, an external toner was prepared. Toner base particles (4) 100 parts by mass, rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment) 1.0 part by mass, silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (4).

(Example 5)
-Production of toner base particles (5)-
Amorphous polymer resin fine particle dispersion (e) 136.7 parts by weight Crystalline resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.4 with a 0.5 mol / l sodium hydroxide aqueous solution, the stainless steel flask was sealed, and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.4 and the electric conductivity was 8.7 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.2 μm, and the particle size distribution coefficient GSD was 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 128.
Further, the viscoelasticity of the toner base particles (5) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 2.5 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 5.0 × 10 ⁴ Pa.

-Preparation of external additive toner (5)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (5), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (5).

(Example 6)
-Production of toner base particles (6)-
Amorphous polymer resin fine particle dispersion (e) 136.7 parts by weight Crystalline resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (i) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.3 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.4 and the electric conductivity reached 7.9 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.9 μm, and the particle size distribution coefficient GSD was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.
Further, the viscoelasticity of the toner base particles (6) was measured using a rotating plate type rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 2.5 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 7.2 × 10 ⁴ Pa.

-Preparation of external additive toner (6)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (6), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (6).

(Example 7)
-Production of toner base particles (7)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by weight Crystalline resin fine particle dispersion (A) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (i) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.7 and the electric conductivity was 11 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.7 μm, and the particle size distribution coefficient GSD was 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.
The viscoelasticity of the toner base particles (7) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). The storage elastic modulus GL (30) at 30 ° C. at an angular frequency of 1 Hz was 2.7 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 3.5 × 10 ⁴ Pa.

-Preparation of external additive toner (7)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (7), 1.0 part by mass of rutile type titanium oxide (average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm, (Silicone oil treatment) After adding 2.0 parts by mass and 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm), using a 5 liter Henschel mixer and blending for 15 minutes at a peripheral speed of 30 m / s Coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (7).

(Example 8)
-Production of toner base particles (8)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by weight Crystalline resin fine particle dispersion (A) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.8 and the electric conductivity was 12 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.9 μm, and the particle size distribution coefficient GSD was 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 131.
Further, the viscoelasticity of the toner base particles (8) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 3.2 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 4.0 × 10 ⁴ Pa.

-Preparation of external additive toner (8)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (8), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by weight, 0.5 parts by weight of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5 liter Henschel mixer. Coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (8).

Example 9
-Production of toner base particles (9)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by weight Crystalline resin fine particle dispersion (A) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (i) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.4 with a 0.5 mol / l sodium hydroxide aqueous solution, the stainless steel flask was sealed, and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.4 and the electric conductivity was 8.2 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.0 μm, and the particle size distribution coefficient GSD was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 129.
Further, the viscoelasticity of the toner base particles (9) was measured using a rotating plate type rheometer (RDA 2RHIOS System Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 3.5 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 6.7 × 10 ⁴ Pa.

-Preparation of externally added toner (9)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (9), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (9).

(Example 10)
-Production of toner base particles (10)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by mass Crystalline resin fine particle dispersion (C) 66.7 parts by mass Colorant dispersion 22.0 parts by weight Release agent dispersion 50. 0 parts by mass or more was sufficiently mixed and dispersed with Ultra-Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.7 and the electric conductivity was 8.8 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.1 μm, and the particle size distribution coefficient GSD was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.
Further, the viscoelasticity of the toner base particles (10) was measured using a rotating plate type rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at 30 ° C. at an angular frequency of 1 Hz was 4.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 7.0 × 10 ⁴ Pa.

-Preparation of external additive toner (10)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (10), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (10).

(Example 11)
-Production of toner base particles (11)-
Amorphous polyester resin fine particle dispersion (g) 136.7 parts by weight Crystalline polyester resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion ( k) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra-Turrax T50 in a round stainless steel flask. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polyester resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.4 with a 0.5 mol / l sodium hydroxide aqueous solution, the stainless steel flask was sealed, and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.9 and the electric conductivity was 11.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.00 μm, and the particle size distribution coefficient GSD was 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 130.
The viscoelasticity of the toner base particles (8) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 2.2 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 2.7 × 10 ⁴ Pa.

—Preparation of External Toner (11) —
Next, an external toner was prepared. 100 parts by mass of toner base particles (11), 1.0 part by mass of rutile type titanium oxide (average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm, (Silicone oil treatment) After adding 2.0 parts by mass and 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm), using a 5 liter Henschel mixer and blending for 15 minutes at a peripheral speed of 30 m / s Coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (11).

(Comparative Example 1)
-Production of toner base particles (12)-
Amorphous polymer resin fine particle dispersion (e) 136.7 parts by mass Crystalline resin fine particle dispersion (B) 66.7 parts by mass Colorant dispersion 22.0 parts by weight Release agent dispersion 50. 0 parts by mass or more was sufficiently mixed and dispersed with Ultra-Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (e) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was further repeated 5 times, and when the pH of the filtrate became 7.5 and the electric conductivity became 7.6 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.8 μm, and the particle size distribution coefficient GSD was 1.26. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 131.
The viscoelasticity of the toner base particles (12) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 1.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 2.0 × 10 ⁴ Pa.

-Preparation of external additive toner (12)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (12), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (12).

(Comparative Example 2)
-Production of toner base particles (13)-
-Amorphous polymer resin fine particle dispersion (g) 250.0 parts by mass-Colorant dispersion 22.0 parts by mass-Release agent dispersion (j) 50.0 parts by mass in a round stainless steel flask Thorough mixing and dispersion was performed with Ultra Turrax T50. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.4 with a 0.5 mol / l sodium hydroxide aqueous solution, the stainless steel flask was sealed, and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.4 and the electric conductivity was 7.7 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.0 μm, and the particle size distribution coefficient GSD was 1.25. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.
The viscoelasticity of the toner base particles (13) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at 30 ° C. at an angular frequency of 1 Hz was 9.8 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 2.0 × 10 ⁵ Pa.

-Preparation of external additive toner (13)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (12), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (13).

(Comparative Example 3)
-Production of toner base particles (14)-
Amorphous polymer resin fine particle dispersion (g) 33.3 parts by mass Crystalline resin fine particle dispersion (B) 183.3 parts by mass Colorant dispersion 22.0 parts by mass Release agent dispersion (j) 50.0 Part by mass The above was sufficiently mixed and dispersed in a round stainless steel flask with Ultra Turrax T50. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate became 7.2 and the electric conductivity became 7.4 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.1 μm, and the particle size distribution coefficient GSD was 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 133.
The viscoelasticity of the toner base particles (14) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 2.5 × 10 ⁷ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 1.5 × 10 ⁴ Pa.

—Preparation of External Toner (14) —
Next, an external toner was prepared. 100 parts by mass of toner base particles (14), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (14).

(Comparative Example 4)
-Production of toner base particles (15)-
Amorphous polymer fine particle dispersion (f) 136.7 parts by weight Crystalline resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j) 50.0 parts by mass or more were sufficiently mixed and dispersed in a round stainless steel flask using Ultra Turrax T50. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer (g) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.4 with a 0.5 mol / l sodium hydroxide aqueous solution, the stainless steel flask was sealed, and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.3 and the electric conductivity was 8.2 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.2 μm, and the particle size distribution coefficient GSD was 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 135.
Further, the viscoelasticity of the toner base particles (15) was measured using a rotating plate type rheometer (RDA 2RHIOS System Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 5.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 3.2 × 10 ⁴ Pa.

-Preparation of external additive toner (15)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (15), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (15).

(Comparative Example 5)
-Preparation of toner base particles (16)-
Amorphous polymer resin fine particle dispersion (h) 136.7 parts by weight Crystalline resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (e) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate reached 7.3 and the electric conductivity reached 12.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 6.0 μm, and the particle size distribution coefficient GSD was 1.24. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 128.
The viscoelasticity of the toner base particles (16) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at 30 ° C. at an angular frequency of 1 Hz was 6.0 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 9.0 × 10 ⁴ Pa.

-Preparation of external additive toner (16)-
Next, an external toner was prepared. 100 parts by mass of toner base particles (16), 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (16).

(Comparative Example 6)
-Production of toner base particles (17)-
Amorphous polymer resin fine particle dispersion (g) 136.7 parts by weight Crystalline resin fine particle dispersion (D) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion (j ) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra Turrax T50 in a round stainless steel flask. Subsequently, 0.20 part by mass of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polymer resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated 5 times, and when the pH of the filtrate was 7.1 and the electric conductivity was 12.0 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.9 μm, and the particle size distribution coefficient GSD was 1.23. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 129.
The viscoelasticity of the toner base particles (17) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). . The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 4.2 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 8.2 × 10 ⁴ Pa.

—Preparation of Externally Added Toner (17) —
Next, an external toner was prepared. Toner mother particles (17) 100 parts by mass, 1.0 part by mass of rutile type titanium oxide (volume average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm) , Silicone oil treatment) 2.0 parts by mass, 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm) was added, and blended for 15 minutes at a peripheral speed of 30 m / s using a 5-liter Henschel mixer. Thereafter, coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (17).

(Comparative Example 7)
-Production of toner base particles (18)-
Amorphous polyester resin fine particle dispersion (g) 136.7 parts by weight Crystalline polyester resin fine particle dispersion (B) 66.7 parts by weight Colorant dispersion 22.0 parts by weight Release agent dispersion ( l) 50.0 parts by mass The above was sufficiently mixed and dispersed with Ultra-Turrax T50 in a round stainless steel flask. Next, 0.20 part by weight of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax. The flask was heated to 46 ° C. with stirring in an oil bath for heating. After maintaining at 46 ° C. for 60 minutes, 66.7 parts by mass of the amorphous polyester resin (f) dispersion was gradually added thereto. Thereafter, the pH of the system was adjusted to 9.5 with a 0.5 mol / l sodium hydroxide aqueous solution, and then the stainless steel flask was sealed and heated to 96 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained.

After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed in 1 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times, and when the pH of the filtrate was 7.5 and the electric conductivity was 12.3 μS / cmt, solid-liquid separation was performed using No5A filter paper by Nutsche suction filtration. Vacuum drying was then continued for 12 hours. When the particle diameter at this time was measured with a Coulter counter, the volume average diameter D50 was 5.8 μm, and the particle size distribution coefficient GSD was 1.26. Moreover, it was observed that the shape factor SF1 of the particle | grains calculated | required from the shape observation by Luzex was 132.
The viscoelasticity of the toner base particles (15) was measured using a rotating plate rheometer (RDA 2RHIOS system Ver. 4.3.2, manufactured by Rheometrics Scientific F.E.). The storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. was 2.5 × 10 ⁸ Pa, and the loss elastic modulus GN (90) at 90 ° C. was 5.0 × 10 ⁴ Pa.

—Preparation of Externally Added Toner (18) —
Next, an external toner was prepared. To 100 parts by mass of toner base particles (18), 1.0 part by mass of rutile type titanium oxide (average particle size 20 nm, n-decyltrimethoxysilane treatment), silica (produced by vapor phase oxidation method, volume average particle size 40 nm, (Silicone oil treatment) After adding 2.0 parts by mass and 0.5 parts by mass of a higher alcohol pulverized product (volume average particle size 8 μm), using a 5 liter Henschel mixer and blending for 15 minutes at a peripheral speed of 30 m / s Coarse particles were removed using a sieve having an opening of 45 μm to prepare an externally added toner (18).

  Tables 2 and 3 show various physical property values of the toners of the externally added toners (1) to (18) prepared as described above.

  The externally added toners (1) to (18) produced as described above were evaluated for minimum fixing temperature, hot offset occurrence temperature, document storage stability, charge amount, and blocking resistance. The results are shown in Tables 4 and 5.

(Evaluation of low-temperature fixability)
5 parts by mass of the externally added toner to be evaluated and 100 parts by mass of ferrite particles (volume average particle size 35 μm) coated with styrene / methyl methacrylate resin (styrene / methyl methacrylate ratio = 50: 50, Mw = 81000) are mixed. Then, a two-component developer was prepared, and this was imaged using a commercially available electrophotographic copying machine (Docu Center Color 400 remodeled machine (manufactured by Fuji Xerox)) to obtain an unfixed image.
Next, the minimum fixing temperature and the hot offset occurrence temperature of the image were evaluated while gradually increasing the fixing temperature between 90 ° C. and 220 ° C. using a belt nip type external fixing machine. The minimum fixing temperature is a fixing temperature at which an unfixed solid image (25 mm × 25 mm) is fixed and then bent using a weight with a constant load, and the degree of image defect of that portion is graded to become a certain grade or higher. Was used as an index of low-temperature fixability. On the other hand, the hot offset occurrence temperature is determined by visually determining the presence or absence of an image defect offset to the position of the second round of the period corresponding to the fixing roll diameter of the toner-fixed image, and the temperature at which the image defect occurs is defined as the hot offset occurrence temperature. .

(Document preservation)
Regarding the evaluation of document storability, after fixing two unfixed images created at the time of the fixing evaluation at 150 ° C. with an external fixing machine, the image portion, the non-image portion, and the image portion overlap each other. It was piled face-to-face, a weight was placed on the overlapped portion so as to be equivalent to 80 g / cm ^2, and left in a constant temperature and humidity chamber at 60 ° C. and 50% humidity for 3 days. After being left, the degree of image loss of the two fixed images superimposed was graded in five stages from “G1” to “G5” shown below.
G1: Since the image portions are adhered to each other, the paper on which the image is fixed is peeled off, the image is severely lost, and the image is clearly transferred to the non-image portion.
G2: Since the images are bonded to each other, white spots of image defects are generated in some parts of the image portion.
G3: When separating the two superimposed images, image blurring and gloss reduction occur on the fixing surfaces of each other, but the image has an acceptable level with almost no image loss. Some transition is seen in the non-image area.
G4: When two superimposed images are separated, a crisp sound is heard and there is a slight image transition in the non-image area, but there is no image loss and there is no problem at all. G5: Both the image area and the non-image There is no image loss or image transfer.

(Evaluation of chargeability)
1.5 parts by mass of the externally added toner to be evaluated and 30 parts by mass of ferrite particles (volume average particle size 35 μm) coated with styrene / methyl methacrylate resin are weighed in a glass bottle with a lid and subjected to high temperature and high humidity (temperature 28). And seasoning for 24 hours under low temperature and low humidity (temperature 10 ° C., humidity 15%), followed by stirring and shaking with a turbula mixer for 5 minutes. The charge amount (μC / g) of the toner in both environments was measured with a blow-off charge amount measuring device.

(Evaluation of blocking properties)
Using a powder tester (manufactured by Hosokawa Micron Corporation), 53 μm, 45 μm, and 38 μm openings are arranged in series from the top, and a toner for developing an electrostatic charge image as a sample is placed on the 53 μm sieve with an amplitude of 1 mm. The vibration was applied for 90 seconds, the toner weight on each sieve after vibration was measured, and the weights of 0.5, 0.3, and 0.1 were added and calculated, and the percentage was calculated. The sample toner (1) was left for about 24 hours in an environment of 50 ° C./50% RH, and the measurement was performed in an environment of 25 ° C./50% RH. In the present invention, the blocking property can be used without any practical problem if the toner weight after vibration is 30% or less, but is preferably 20% or less, more preferably 10% or less.

From Tables 4 and 5, by using the electrostatic charge image developing toners of Examples 1 to 11, it has excellent low-temperature fixability and can achieve both document storage stability, chargeability, and blocking resistance. It turns out that it is possible.
On the other hand, in Comparative Example 1, the amorphous polymer resin having a relatively high compatibility is used as the binder resin, and the surface layer resin is also compatible with the crystalline resin by using the same amorphous polymer for the surface layer. As a result, although the low-temperature fixability is excellent, the document storage stability and blocking resistance are deteriorated. In Comparative Example 2, since the crystalline resin is not used, the sharp melt property is impaired, and the low temperature fixability is difficult. In Comparative Example 3, it was confirmed that the strength of the fixed image, particularly the scratch strength, was lowered at the same time as the chargeability under high temperature and high humidity was lowered by using an excessive crystalline resin. In Comparative Example 4, an amorphous polymer resin having higher compatibility than the binder resin was added to the surface layer of the toner particles, but this deteriorated document storage stability and blocking resistance. In Comparative Example 5, since a resin having a relatively high softening point was used for the amorphous polymer used for the binder resin, low-temperature fixing was difficult. In Comparative Example 6, a crystalline resin having a high melting point (endothermic peak temperature) was used, but this was also difficult to fix at a low temperature. Comparative Example 7 uses a paraffin wax having a small SP value, but has low compatibility with the amorphous polyester resin used for the binder resin, and the wax is exposed on the surface of the toner particles. Separation from the toner was confirmed, and the charge level of the toner decreased.

Claims (7)

A crystalline resin A and an amorphous polymer B are included as a binder resin, and the surface is coated with a surface layer mainly composed of an amorphous polymer C different from the amorphous polymer B. Further, a release agent D An electrostatic charge image developing toner in which the amorphous polymer B is an amorphous polyester resin B ′ ,
The endothermic peak temperature TmA [° C.] derived from the crystalline resin A, the endothermic peak TmAB [° C.] derived from the crystalline resin A when the crystalline resin A and the amorphous polymer B are mixed, and the crystalline resin the endothermic peak temperature TmAC derived from crystal resin a [° C.] when mixed with a and amorphous polymer C, but meets the following relationship formula (1),
A solubility parameter SP _B of the amorphous polymer B, a solubility parameter SP _D of the releasing agent D, but the relationship of the following equation (3) satisfies,
The endothermic peak temperature of the crystalline resin A is 60 to 80 ° C.,
An electrostatic charge image developing toner, wherein the content of the crystalline resin A is 5 to 50% by mass .
TmAB <TmAC ≦ TmA Formula (1)
_{· 0.8 <SP B - SP D} <1.8 ··· formula (3) SP is the solubility parameter of the crystalline resin A. _A And the solubility parameter of the amorphous polymer C is SP _C 2. The electrostatic charge image developing toner according to claim 1, wherein the following relation (2) is satisfied.
・ SP _D   <SP _A   <SP _B   <SP _C   ... Formula (2)   In the differential scanning calorimetry curve obtained by the differential scanning calorimeter measurement, the endothermic peak derived from the crystalline resin A and the endothermic peak derived from the release agent D in the temperature range of 50 to 100 ° C. in the first temperature rising process. The sum E of the absolute values of the calories is larger than the sum F of the absolute values of the endothermic peaks derived from the crystalline resin A and the endothermic peaks derived from the release agent D in the second temperature raising process after cooling. The toner for developing an electrostatic image according to claim 1, wherein the toner is for developing an electrostatic image. The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the amorphous polymers B and C have a softening point of 80 to 130 ° C. The electrostatic image developing toner according to claim 1, wherein the crystalline resin A is a crystalline polyester. Storage elastic modulus GL (30) at an angular frequency of 1 Hz and 30 ° C. is 1 × 10 ⁷ It is Pa or more, and the loss elastic modulus GN (90) at 90 ° C. is 1.0 × 10 ⁵ The toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the toner is Pa or less. A method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6 ,
A mixed dispersion is prepared by mixing a crystalline resin A fine particle dispersion in which crystalline resin A fine particles are dispersed and an amorphous polymer B fine particle dispersion in which amorphous polymer B fine particles are dispersed. After adding a polymer of one or more metal salts containing, and forming aggregated particles at a temperature lower than the endothermic peak temperature of the crystalline resin A fine particles when the mixed dispersion is measured with a differential scanning calorimeter, An agglomerated fine particle dispersion production process for producing an agglomerated fine particle dispersion obtained by agglomerating and growing the agglomerated particles;
An adhesion step of adhering amorphous polymer C fine particles to the surface of the aggregated fine particles by adding and mixing an amorphous polymer C fine particle dispersion in which amorphous polymer C fine particles are dispersed in the aggregated fine particle dispersion;
By making the pH of the aggregated fine particle dispersion liquid that has undergone the adhesion step basic, the growth of the aggregated fine particles is stopped, and the fusion / unification step of fusing and coalescing by heating this,
A method for producing a toner for developing an electrostatic charge image, comprising: