JP2011164333A - Toner for electrostatic charge image development, method for producing toner for electrostatic charge image development, developer for electrostatic charge image development, toner cartridge, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development, the toner suppressing generation of gloss irregularity even when an image is formed on a sheet having a large degree of surface roughness. <P>SOLUTION: The toner for electrostatic charge image development contains a resin and a release agent, wherein when the storage modulus of the toner by dynamic viscoelastic measurement at a frequency of 6.28 Rad is denoted by G'(100) and G'(200) at 100°C and 200°C, respectively, G'(100)/G'(200) ranges from 1 to 5. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner, an electrostatic image developing toner manufacturing method, an electrostatic image developing developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic latent image is formed on an image carrier by a charging and exposure process (latent image forming process), and an electrostatic charge image developing toner (hereinafter sometimes simply referred to as “toner”). The electrostatic latent image is developed with a developer for developing an electrostatic charge image (hereinafter sometimes referred to simply as “developer”) (development process), and visualized through a transfer process and a fixing process. The developer used here includes a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a nonmagnetic toner alone.

  In recent years, a toner manufacturing method using a wet manufacturing method such as an emulsion polymerization aggregation method has been proposed as a means capable of intentionally controlling the shape and surface structure of the toner. In the emulsion polymerization aggregation method, a resin particle dispersion is generally produced by emulsion polymerization or the like, while a colorant dispersion in which a colorant is dispersed in a solvent, a release agent dispersion in which a release agent is dispersed in a solvent, and the like. Thereafter, these are mixed to form agglomerated particles corresponding to the toner particle diameter, and the toner is fused and united by heating to obtain a toner.

  On the other hand, by using a fixing roll having high thermal conductivity in the fixing process of electrophotography, heat loss during fixing is suppressed and environmental load is reduced.

  For example, in Patent Document 1, for the purpose of providing a heat conducting member having an increased thermal conductivity without impairing the elasticity of the elastic layer, the rotation has an elastic layer and passes through the elastic layer to transfer heat. In the heat conduction member comprising a body, the elastic layer has a relatively high thermal conductivity and a relatively hard heat conductive material, and a relatively low heat conductivity and a relatively soft elasticity. There is described a heat conducting member characterized in that the regions are scattered.

Further, Patent Document 2 does not have a wait time after power-on, and enables high-speed fixing using an on-demand type heating and fixing device that does not require standby preliminary heating, and generates a low temperature offset and a high temperature offset. In order to provide a toner having sufficient fixability, an image forming method and an apparatus, a heating metal sleeve, and the heating metal sleeve disposed in contact with the inner surface of the heating metal sleeve are provided. A fixing unit having at least a heating member to be heated and a rotatable pressure member that is in pressure contact with the heating member via the heating metal sleeve and has a rotation axis parallel to the heating metal sleeve; An unfixed toner image was formed on the fixing nip formed by press-contacting the heating metal sleeve and the pressure member. A toner used in an image forming method having a fixing step of fixing the unfixed toner image on the recording material by passing the recording material, and containing at least a binder resin, a colorant, and a wax, The maximum endothermic peak of the endothermic curve obtained by measurement with a differential scanning calorimeter (DSC) is in the range of 60 to 135 ° C., and the temperature at which the loss modulus G ″ is 3 × 10 ⁴ Pa is 90 to 115 ° C. And a temperature at which the loss elastic modulus G ″ is 2 × 10 ⁴ Pa is 95 to 120 ° C. and the temperature at which the loss elastic modulus G ″ is 1 × 10 ⁴ Pa is 105 to 135 ° C. ing.

Patent Document 3 provides a full-color image forming apparatus and a full-color image forming method using a full-color toner that obtains an appropriate gloss and does not cause offset or paper wrapping without oil application to a fixing device. For this purpose, an electrophotographic full-color image forming apparatus comprising a full-color toner having at least a binder resin and a colorant and a fixing device having a fixing temperature in a range of 140 to 200 ° C. The full-color toner uses a styrene-acrylic resin as a binder resin and has at least one peak in the (weight average) molecular weight distribution measured by GPC, and has a molecular weight of 6 × 10 ^{3 to} 6 The ratio of components having a main peak in the region of × 10 ⁴ and a molecular weight of 1 × 10 ³ or less to the total toner Is 10% by weight or less, the proportion of the component having a molecular weight of 2 × 10 ⁵ or more in the total toner is 7% by weight or less, the weight average molecular weight is Mw, and the number average molecular weight is Mn, Mw / Mn The value is 2 ≦ Mw / Mn ≦ 15, the toner softening point is Tm (° C.), and the DSC curve measured by the differential scanning calorimeter of the toner shows the endothermic peak at the time of temperature rise corresponding to the release agent. When the peak temperature is Wp (° C.), 10 ≦ Tm−Wp ≦ 60, and when a solid image is formed, the glossiness in the solid image (according to JIS-Z874160-degree specular gloss measurement method) A full-color image forming apparatus having a value in the range of 7 to 20 is described.

  Patent Document 4 discloses an electrostatic charge image that has good image peelability from a fixing member even in the formation of an image with a small margin at the tip of a recording medium, forms a high-gloss image, and has good offset resistance. For the purpose of providing a developing toner, it contains a crystalline polyester resin, an amorphous polyester resin, an aluminum element, a tin element, and a release agent. 005% by mass to 0.060% by mass, the content of the tin element is 0.12% by mass to 0.72% by mass with respect to the whole toner, and the acid value of the release agent is 0 mgKOH The toner for developing an electrostatic charge image is described in the range of / g to 5.0 mgKOH / g.

Japanese Patent Laid-Open No. 2005-084077 JP 2004-151438 A JP 2007-293359 A JP 2009-122522 A

  The present invention relates to an electrostatic charge image developing toner capable of suppressing the occurrence of uneven glossiness even when an image is formed on a sheet having a large surface unevenness, a method for producing the electrostatic charge image developing toner, and the electrostatic charge image developing toner. And a developer for developing an electrostatic charge image, a toner cartridge, a process cartridge, and an image forming apparatus.

  The invention according to claim 1 includes a resin and a release agent, and the storage elastic modulus at 100 ° C. is G ′ (100) and the storage elastic modulus at 200 ° C. is G ′ in the measurement of toner frequency 6.28 Rad dynamic viscoelasticity. (200) is a toner for developing electrostatic images in which G ′ (100) / G ′ (200) is in the range of 1 to 5.

  According to a second aspect of the present invention, in the differential thermal analysis of the toner, the endothermic peak temperature of the release agent is in the range of 50 ° C. to 80 ° C., and the peak height from the baseline in the endothermic peak of the release agent. 2. The electrostatic image developing toner according to claim 1, wherein a temperature range of a line drawn parallel to the base line at a height of 10% is in a range of 10 ° C. or more and 20 ° C. or less.

  The invention according to claim 3 is the electrostatic image developing toner according to claim 1 or 2, wherein the acid value of the release agent is in the range of 3 mgKOH / g to 10 mgKOH / g.

  According to a fourth aspect of the present invention, in the differential thermal analysis of the toner, the difference between the endothermic peak temperature and the exothermic peak temperature of the release agent is in the range of 5 ° C. or higher and 20 ° C. or lower. The toner for developing an electrostatic charge image according to any one of the above items.

  The invention according to claim 5 is a resin particle / release agent mixed dispersion preparation step of preparing a resin particle / release agent mixed dispersion in which resin particles containing a resin and a release agent are melt-mixed and dispersed; A mixing step of mixing the resin particle / release agent mixed dispersion and a colorant dispersion in which a colorant is dispersed to form aggregated particles; and a fusion step of heating and aggregating the aggregated particles. The method for producing a toner for developing an electrostatic charge image according to claim 1.

  The invention according to claim 6 is an electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to any one of claims 1 to 4 and a carrier.

  A seventh aspect of the present invention is a toner cartridge containing the electrostatic image developing toner according to any one of the first to fourth aspects.

  According to an eighth aspect of the present invention, there is provided the image carrier, and a developing unit that develops the electrostatic latent image formed on the surface of the image carrier using a developer to form a toner image. The agent is a process cartridge which is the developer for developing an electrostatic image according to claim 6.

  According to a ninth aspect of the present invention, there is provided an image carrier, latent image forming means for forming an electrostatic latent image on the surface of the image carrier, and developing the electrostatic latent image with a developer to form a toner image. The image forming apparatus according to claim 6, further comprising: a developing unit that forms; and a transfer unit that transfers the developed toner image to a transfer target, wherein the developer is an electrostatic charge image developing developer according to claim 6. is there.

  According to a tenth aspect of the present invention, there is provided a residual toner removing unit that removes residual toner remaining on the surface of the image carrier after the transfer, a residual toner removed by the residual toner removing unit, and the recovered residual The image forming apparatus according to claim 9, further comprising: a residual toner collecting / supplying unit that supplies toner to the developing unit.

  According to the first aspect of the present invention, even when an image is formed on a sheet having a large surface unevenness as compared with the case where G ′ (100) / G ′ (200) is outside the range of 1 or more and 5 or less, uneven gloss is produced. The present invention provides a toner for developing an electrostatic charge image in which the generation of toner is suppressed.

  According to claim 2 of the present invention, the endothermic peak temperature of the release agent is outside the range of 50 ° C. or more and 80 ° C. or less, and the temperature range is outside the range of 10 ° C. or more and 20 ° C. or less. The present invention also provides an electrostatic charge image developing toner that suppresses the occurrence of uneven glossiness even when an image is formed on a sheet having a large surface unevenness.

  According to the third aspect of the present invention, uneven glossiness is obtained even when an image is formed on a paper having a large surface roughness, as compared with a case where the acid value of the release agent is outside the range of 3 mgKOH / g or more and 10 mgKOH / g or less. The present invention provides a toner for developing an electrostatic charge image in which the generation of toner is suppressed.

  According to the fourth aspect of the present invention, an image is formed on a sheet having a large surface irregularity as compared with the case where the difference between the endothermic peak temperature and the exothermic peak temperature of the release agent is outside the range of 5 ° C. or more and 20 ° C. or less. Provided is a toner for developing an electrostatic image in which the occurrence of uneven glossiness is suppressed even when formed.

  According to claim 5 of the present invention, it does not include a resin particle / release agent mixed dispersion preparation step of preparing a resin particle / release agent mixed dispersion in which resin particles and a release agent are melt-mixed and dispersed. The present invention provides a method for producing a toner for developing an electrostatic charge image, which can provide a toner for developing an electrostatic charge image in which the occurrence of uneven glossiness is suppressed even when an image is formed on a sheet having a large surface unevenness.

  According to the sixth aspect of the present invention, uneven glossiness is obtained even when an image is formed on a sheet having a large surface unevenness as compared with the case where G ′ (100) / G ′ (200) is outside the range of 1 to 5. Provided is a developer for developing an electrostatic charge image in which the occurrence of is suppressed.

  According to the seventh aspect of the present invention, uneven glossiness is obtained even when an image is formed on a sheet having a large surface roughness as compared with the case where G ′ (100) / G ′ (200) is outside the range of 1 to 5. Provided is a toner cartridge in which occurrence of the toner is suppressed.

  According to the eighth aspect of the present invention, uneven glossiness is obtained even when an image is formed on a paper having a large surface roughness as compared with the case where G ′ (100) / G ′ (200) is outside the range of 1 to 5. Provided is a process cartridge in which the occurrence of the above is suppressed.

  According to the ninth aspect of the present invention, uneven glossiness is obtained even when an image is formed on a sheet having a large surface roughness as compared with the case where G ′ (100) / G ′ (200) is outside the range of 1 to 5. Provided is an image forming apparatus in which the occurrence of the above is suppressed.

  According to the tenth aspect of the present invention, there is provided an image forming apparatus in which the toner for developing an electrostatic image is easily collected and reused, and the toner is used for a long period of time.

It is a schematic structure figure showing an example of a process cartridge concerning an embodiment of the present invention. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an embodiment of the present invention.

  Embodiments of the present invention will be described below. This embodiment is an example for carrying out the present invention, and the present invention is not limited to this embodiment.

  The toner for developing an electrostatic charge image according to the embodiment of the present invention includes a resin and a release agent. In the toner according to the exemplary embodiment, when the storage elastic modulus at 100 ° C. in the toner frequency 6.28 Rad dynamic viscoelasticity measurement is G ′ (100) and the storage elastic modulus at 200 ° C. is G ′ (200), G '(100) / G' (200) is in the range of 1 to 5. When the G ′ (100) / G ′ (200) of the toner is in the range of 1 or more and 5 or less, the present inventors suppress the occurrence of uneven gloss even when an image is formed on a sheet having large surface irregularities. I found out. By setting G ′ (100) / G ′ (200) in the range of 1 to 5 in the fixing step, the fixing is performed when the toner image is fixed on a transfer medium such as paper by a fixing member such as a fixing roll. Regardless of unevenness of temperature, pressure, etc. of the member, the toner melts to a certain level without variation, so the surface step of the toner image becomes small. For example, when an image is formed on a paper with a large surface roughness of 3.0 μm or more However, the occurrence of uneven gloss is considered to be suppressed. If G ′ (100) / G ′ (200) is less than 1, when the low-temperature elastic modulus is high, the gloss of the low-temperature part of the paper is difficult to be obtained or the adhesion to the paper is insufficient. , Image strength tends to decrease. Further, when the elastic modulus on the high temperature side is high, the release rate of the release agent is lowered, and the releasability of the fixed image from the fixing roll is lowered. On the other hand, if it exceeds 5, the elastic modulus lowers on the high temperature side and the gloss increases, and image defects such as streaks and black spots due to fusing roll stains become prominent in long-term use. G ′ (100) / G ′ (200) is preferably in the range of 1.0 or more and 4.0 or less.

  For example, when G ′ (100) / G ′ (200) is controlled within the above range, the weight average molecular weight of the resin in the toner is in the range of 30,000 to 700,000 in the case of crystalline resin. In the case of a crystalline resin, a method in which the range is from 50,000 to 150,000, a crosslinking agent such as an amino resin such as isocyanate or melamine, or a divalent or higher valent metal salt such as calcium, magnesium, barium, iron, or aluminum. By using a method of crosslinking the resin, a method of adding particles such as alumina, silica, titania and the like, a method of crosslinking by radicals, ionic crosslinking, crosslinking by oxidation reaction, etc. for unsaturated polyester resins, and combinations thereof The G ′ (100) / G ′ (200) of the toner may be within the above range. Among these, a combination of a method for adjusting the molecular weight of the crystalline resin and the amorphous resin in the toner to an appropriate range, a method for crosslinking with a metal salt having a valence of 2 or more, and a method for adding inorganic fine particles are preferable.

  In the toner according to the present embodiment, in the differential thermal analysis (DSC) of the toner, the endothermic peak temperature of the release agent is in the range of 50 ° C. to 80 ° C., and the peak height from the baseline in the endothermic peak of the release agent. It is preferable that the temperature width of a line drawn parallel to the base line at a height of 10% is in the range of 10 ° C. or more and 20 ° C. or less. By setting the endothermic properties of the release agent within the above range, low temperature components in the release agent are easily eluted even at a relatively low temperature or low pressure, and high temperature components are easily eluted at a relatively high temperature or pressure. Therefore, even if temperature unevenness or pressure unevenness occurs at the interface between the toner image and the fixing member such as the fixing roll, the release agent oozes out almost uniformly, so that uneven heat from the fixing roll to the toner image is suppressed. Therefore, it is considered that contact at the interface between the toner image and the fixing roll becomes almost uniform, and uneven gloss is suppressed. If the endothermic peak temperature of the release agent is less than 50 ° C., the release agent may be eluted even at the temperature in the actual apparatus. If it exceeds 80 ° C., the melting is insufficient, and it is difficult to elute at the lower limit of the fixing temperature. There is a case where a defect occurs on an image in a long-term use such as a tendency, peeling failure, and fixing roll contamination due to non-visual offset. If the temperature range at the endothermic peak of the release agent is less than 10 ° C., the crystallinity tends to be too high, and the unevenness of the release agent exposed on the surface of the image may be uneven. Further, since it becomes difficult to encapsulate the toner particles, the toner powder fluidity may be deteriorated by the surface-exposed release agent, or the released release agent may form a film on the photosensitive member to generate black stripes. is there. When it exceeds 20 ° C., the release agent has low crystallinity and tends to be soft. In this case, there may be a problem in the strength of the image, or there may be a component that plasticizes with the resin in the toner particles themselves, which is a problem for achieving stabilization of the toner particles and high storage stability. There is. The endothermic peak temperature of the release agent is in the range of 60 ° C. or higher and 75 ° C. or lower, and the temperature range of the line drawn parallel to the baseline at the height of 10% of the peak height from the baseline at the endothermic peak of the release agent Is more preferably in the range of 12 ° C. or higher and 18 ° C. or lower, and further preferably in the range of 13 ° C. to 17 ° C.

  In the toner according to the exemplary embodiment, the acid value of the release agent is preferably in the range of 3 mgKOH / g to 10 mgKOH / g. When the acid value of the release agent is in the range of 3 mgKOH / g or more and 10 mgKOH / g or less, when the toner image is fixed, the exposure of the release agent to the surface of the toner image is moderated, so that the fixing member such as a fixing roll can be used. It is considered that an appropriate amount of the release agent is transferred, and the release agent is almost uniformly oozed out without being substantially affected by the amount of biting (nip) between the fixing member and the transferred member. If the acid value of the release agent is less than 3 mgKOH / g, the toner may be unevenly distributed inside the toner, and the elution rate may be slow. If it exceeds 10 mgKOH / g, it is more unevenly distributed on the toner surface, so the elution rate is improved, but there is a concern about the inclusion in the toner, the fluidity in the toner particles, the charging stability, etc. May occur. The acid value of the release agent is more preferably from 4 mgKOH / g to 9 mgKOH / g, and still more preferably from 5 mgKOH / g to 8 mgKOH / g.

  In the toner according to the exemplary embodiment, the difference between the endothermic peak temperature and the exothermic peak temperature of the release agent is preferably in the range of 5 ° C. to 20 ° C. in the differential thermal analysis (DSC) of the toner. By setting the difference between the endothermic peak temperature and the exothermic peak temperature of the release agent within the above range, the release agent slowly recrystallizes after fixing the toner image. It is thought that recrystallization causes a decrease in gloss and suppresses occurrence of uneven gloss. When the difference between the endothermic peak temperature and the exothermic peak temperature of the release agent is less than 5 ° C, the gloss is partially lowered due to the temperature drop of the part rubbed by the peeling member that peels off the image surface that has passed through the fixing machine. If the temperature exceeds 20 ° C., the strength of the fixed image tends to decrease, and the image may be easily damaged. The difference between the endothermic peak temperature and the exothermic peak temperature of the release agent is more preferably in the range of 7 ° C to 18 ° C, and further preferably in the range of 9 ° C to 16 ° C.

  The toner for developing an electrostatic charge image according to the embodiment of the present invention contains at least one of a crystalline resin and an amorphous resin as a resin and a release agent, and optionally contains a colorant.

  In the present embodiment, “crystallinity” of “crystalline resin” refers to having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning calorimetry (DSC) of the resin or toner. Specifically, in differential scanning calorimetry (DSC) using a differential scanning calorimeter (equipment name: DSC-60 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, a rate of temperature increase of 10 ° C./min. A “clear” endothermic peak is assumed when the temperature from the onset point to the top of the endothermic peak when the temperature is raised at 10 ° C. is within 10 ° C. Further, from the viewpoint of sharp melt, the temperature from the onset point to the peak top of the endothermic peak is preferably within 10 ° C, and more preferably within 6 ° C. Specify any point on the flat part of the baseline in the DSC curve and any point on the flat part of the falling part from the baseline, and the intersection of the tangents of the flat part between the two points is automatically set as the “onset point”. Obtained automatically by the tangent processing system. Further, the endothermic peak may show a peak having a width of 40 ° C. or more and 50 ° C. or less when the toner is used.

  Further, the “amorphous resin” used as the binder resin means that when the temperature from the onset point to the peak top of the endothermic peak exceeds 10 ° C. in the differential scanning calorimetry (DSC) of the resin or toner, or clearly It indicates that the resin does not show a significant endothermic peak. Specifically, in differential scanning calorimetry (DSC) using a differential scanning calorimeter (equipment name: DSC-60 type) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system, a rate of temperature increase of 10 ° C./min. When the temperature from the onset point to the top of the endothermic peak when the temperature is raised at 10 ° C. exceeds 10 ° C., or when no clear endothermic peak is observed, it is assumed to be “amorphous”. Further, the temperature from the onset point to the peak top of the endothermic peak preferably exceeds 12 ° C., and more preferably no clear endothermic peak is observed. The method for obtaining the “onset point” in the DSC curve is the same as in the case of the “crystalline resin”.

  As the crystalline resin, any resin having any crystallinity as defined above may be used. Specific examples include crystalline polyester resins and crystalline vinyl resins, but crystalline polyester resins are preferred from the viewpoints of adhesion to paper and charging during fixing, and adjustment of melting temperature within a preferred range. . An aliphatic crystalline polyester resin having an appropriate melting temperature is more preferable.

  Crystalline vinyl resins include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate, etc. Examples thereof include vinyl resins using long-chain alkyl or alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means that both “acryl” and “methacryl” are included.

  On the other hand, the crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In this embodiment, the “acid-derived constituent component” refers to a component before synthesis of the polyester resin. The component part which was an acid component is pointed out, and the "alcohol-derived component" refers to the component part which was an alcohol component before the synthesis of the polyester resin.

  When the polyester resin is not crystalline, that is, amorphous, the toner blocking resistance and image storability may not be maintained while ensuring good low-temperature fixability. In the case of a polymer in which other components are copolymerized with respect to the crystalline polyester main chain, when the other components are 50% by weight or less, this copolymer is also called a crystalline polyester resin.

[Acid-derived components]
The acid-derived constituent component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, Acid anhydrides can be mentioned but are not limited to these. Among the aliphatic dicarboxylic acids, in view of availability, sebacic acid and 1,10-decanedicarboxylic acid are preferable.

  As the acid-derived constituent component, in addition to the aforementioned aliphatic dicarboxylic acid-derived constituent component, it is preferable that a constituent component such as a dicarboxylic acid-derived constituent component having a double bond is included. The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included.

  A dicarboxylic acid having a double bond is preferably used in order to prevent hot offset at the time of fixing, because the entire resin can be crosslinked using the double bond. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

  The content of the acid-derived constituent components other than these aliphatic dicarboxylic acid-derived constituent components (dicarboxylic acid-derived constituent components having a double bond) in the acid-derived constituent components is 1 constituent mol% or more and 20 constituent mol% or less. Preferably, 2 component mol% or more and 10 component mol% or less are more preferable.

  When the content is less than 1 component mol%, pigment dispersion may not be good or the emulsion particle size may become large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting temperature is lowered, the storage stability of the image is deteriorated, or the emulsion particle size is too small to dissolve in water, resulting in latex. There may not be. In the present specification, “constituent mol%” refers to a percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is defined as one unit (mol).

[Alcohol-derived components]
The alcohol-derived constituent component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane. Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecane Examples include, but are not limited to, diol, 1,18-octadecanediol, 1,20-eicosanediol, and the like. Among the aliphatic diols, 1,9-nonanediol and 1,10-decanediol are preferable in view of the melting temperature and resistance of the resin.

  The alcohol-derived constituent component preferably has an aliphatic diol-derived constituent component content of 80 constituent mol% or more, and may contain other components as necessary. As the alcohol-derived constituent component, the content of the aliphatic diol-derived constituent component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. On the other hand, examples of other components included as necessary include components such as a diol-derived component having a double bond and a diol-derived component having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. On the other hand, as the diol having a sulfonic acid group, 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, 2-sulfo-1,4-butane Examples include diol sodium salt.

  Alcohol-derived components in the case of adding alcohol-derived components other than these linear aliphatic diol-derived components (diol-derived component having a double bond and / or diol-derived component having a sulfonic acid group) As content in a component, 1 to 20 component mol% is preferable, and 2 to 10 component mol% is more preferable. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting temperature is lowered, the storage stability of the image is deteriorated, or the emulsion particle size is too small to dissolve in water, resulting in latex. There may not be.

  The production method of the polyester resin is not particularly limited, and may 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. It can be manufactured separately depending on the type. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The production of the polyester resin may be performed, for example, at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and the reaction system may be reduced in pressure as necessary and reacted while removing water and alcohol generated during condensation. Good. When the monomer is not dissolved or compatible at 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 may be 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 may be condensed in advance and then polycondensed together with the main component.

  Catalysts that may be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, germanium, and the like. Metal compounds; phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like.

  In addition to the polymerizable monomers described above for the purpose of adjusting the melting temperature, molecular weight, etc. of the crystalline resin that is the main component of the binder resin in the present embodiment, shorter chain alkyl groups, alkenyl groups, aromatic rings A compound having the above may be used. Specific examples include dicarboxylic acids, alkyl dicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2,6- Examples include aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, and nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid. Short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc. In the case of short chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, (meth) Short chain alkyls such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, alkenyl (meth Acrylic esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene, isoprene, etc. Olefins and the like. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In the present embodiment, a compound having a hydrophilic polar group may be used as long as it is copolymerizable as a resin for an electrostatic charge image developing toner. As a specific example, when the resin used is a polyester, a dicarboxylic acid compound in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted with a sulfonyl group is used. In the case of a resin, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, zinc mono (meth) acrylate, zinc di (meth) acrylate, Esters of (meth) acrylic acid and alcohols such as 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate, sulfonyl groups at any of the ortho, meta, and para positions Have Derivatives of styrene, sulfonyl group-substituted aromatic vinyl such as sulfonyl group-containing vinyl naphthalene.

  The weight average molecular weight Mw of the crystalline resin is preferably 30,000 or more, and more preferably 35,000 or more and 70,000 or less. When the polymer has high crystallinity and contains a polymer binder resin, it becomes a toner having a high hardness and is excellent in rubbing properties. If the weight average molecular weight Mw of the crystalline resin is less than 30,000, the number of molecules of the crystalline resin per toner weight increases, and the charging characteristics derived from the bonds between the molecules of the crystalline resin may decrease. Since the toner particles are easily separated from the toner particles, problems derived from the released resin (filming, increase in fine powder due to brittleness, deterioration in powder fluidity, etc.) may occur. As described above, the weight average molecular weight Mw of the crystalline resin is preferably in the range of 30,000 to 70,000 in order to make G ′ (100) / G ′ (200) of the toner within the above range.

  The amorphous resin used in the toner according to the exemplary embodiment is not particularly limited. Specifically, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic acid acrylic monomers such as n-propyl, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc. Methacrylic monomers; Ethylene unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrenesulfonate; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether Kind Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; homopolymers of olefin monomers such as ethylene, propylene and butadiene, copolymers obtained by combining two or more of these monomers, or Mixtures thereof, furthermore, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, etc., non-vinyl condensation resins, or mixtures thereof with the vinyl resins, in the presence of these Examples include graft polymers obtained by polymerizing vinyl monomers. These resins may be used alone or in combination of two or more. Of these resins, styrene resins and acrylic resins are particularly preferable.

  The weight average molecular weight (Mw) of the amorphous resin is preferably in the range of 50,000 to 500,000, more preferably in the range of 70,000 to 450,000. If the Mw is less than 50,000, an offset may occur at the time of high-temperature fixing or use in a thermally stressed condition such as thin paper, low image coverage, and heating time length (slow process speed). The strength may deteriorate, and if it exceeds 500,000, the low-temperature fixability may deteriorate, or the gloss of the fixed image may decrease. The number average molecular weight (Mn) of the amorphous resin is preferably in the range of 10,000 to 40,000, and more preferably in the range of 12,000 to 35,000. If Mn is less than 10,000, the strength of the fixed image may be reduced, and if it exceeds 40,000, the low-temperature fixability may be deteriorated or the gloss of the fixed image may be reduced. As described above, in order to make G ′ (100) / G ′ (200) of the toner within the above range, the weight average molecular weight Mw of the amorphous resin is more preferably from 70,000 to 200,000, A range of 000 to 150,000 is particularly preferable.

  Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene, polybutene, silicones having a softening point by heating, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc. Fatty acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, fisher Minerals such as Tropsch wax and the like, petroleum-based waxes, and modified products thereof can be used.

  Among these, the endothermic peak temperature in the differential thermal analysis is in the range of 50 ° C. or more and 80 ° C. or less, preferably the difference between the endothermic peak temperature and the exothermic peak temperature is in the range of 5 ° C. or more and 20 ° C. or less, Moreover, what is necessary is just to select what has an acid value of the range of 3 mgKOH / g or more and 10 mgKOH / g or less.

  In this embodiment, as the release agent, the temperature range of a line drawn in parallel with the baseline at a height of 10% of the peak height from the baseline at the endothermic peak of the differential thermal analysis of the release agent is 10 ° C. or more and 20 ° C. Those within the range of ° C. or lower may be selected, or those within the above range may be obtained by purification treatment or the like. The purification method is not particularly limited, and examples thereof include a reprecipitation method (recrystallization method, melt recrystallization method), column purification method, solvent extraction, fractional distillation and the like.

  These mold release agents can be used alone or in combination of two or more. The content of these release agents is preferably 1 part by weight or more and 10 parts by weight or less, and more preferably 5 parts by weight or more and 9 parts by weight or less with respect to 100 parts by weight of the binder resin.

  The colorant used in the toner of the exemplary embodiment may be a dye or a pigment, but a pigment is preferable from the viewpoint of light resistance and water resistance. Preferred pigments include carbon black, aniline black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, Quinacridone, benzidine yellow, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 185, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. A known pigment such as CI Pigment Blue 15: 3 may be used. Moreover, you may use magnetic powder as a coloring agent. As the magnetic powder, a known magnetic material such as a ferromagnetic metal such as cobalt, iron or nickel, an alloy of metal such as cobalt, iron, nickel, aluminum, lead, magnesium, zinc or manganese, or an oxide may be used. .

  These can be used alone or in combination of two or more. The content of these colorants is preferably from 0.1 to 40 parts by weight, more preferably from 1 to 30 parts by weight, based on 100 parts by weight of the binder resin.

  In addition, each color toner such as yellow toner, magenta toner, cyan toner, and black toner can be obtained by appropriately selecting the type of the colorant.

  There is no restriction | limiting in particular as another component, What is necessary is just to select suitably according to the objective, For example, well-known various additives, such as an inorganic particle and a charge control agent, etc. are mentioned.

  If necessary, inorganic particles may be added to the toner of this embodiment. As the inorganic particles, known inorganic particles such as silica particles, titanium oxide particles, alumina particles, cerium oxide particles, or those whose surfaces have been subjected to a hydrophobic treatment may be used alone or in combination of two or more types. Silica particles having a refractive index smaller than that of the binder resin are preferred from the standpoint of not impairing transparency such as transparency and OHP permeability. Further, the silica particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferable.

  By adding these inorganic particles, the viscoelasticity of the toner may be adjusted, and the glossiness of the image and the penetration into the paper may be adjusted. The inorganic particles are preferably contained in an amount of 0.5% to 20% by weight, more preferably 1% to 15% by weight, based on 100 parts by weight of the toner raw material.

  A charge control agent may be added to the toner of the exemplary embodiment as necessary. As the charge control agent, a chromium-based azo dye, an iron-based azo dye, an aluminum azo dye, a salicylic acid metal complex, or the like may be used.

<Method for producing toner for developing electrostatic image>
The toner according to the exemplary embodiment is preferably manufactured by a wet manufacturing method such as an emulsion polymerization aggregation method (aggregation / unification method).

  The method for producing an electrostatic charge image developing toner according to the present embodiment includes, for example, a resin particle dispersion in which resin particles are dispersed, a colorant dispersion in which a colorant is dispersed, and a release agent dispersion in which a release agent is dispersed. An aggregating step of mixing the liquid to form aggregated particles containing resin particles, a release agent and a colorant; a stopping step of adjusting the pH in the aggregated system to stop the aggregation growth of the aggregated particles; and the aggregated particles Is a method including a fusing step of heating and fusing the resin particles to a temperature equal to or higher than the melting point of the resin particles or the glass transition temperature, and a washing step of washing the toner particles obtained by fusing with at least water. You may further have a drying process which dries a toner particle. Moreover, you may have the shell layer formation process of adding the same or different resin particle after the aggregation process, and making it adhere to the surface of an aggregate particle as needed.

  In the present embodiment, a method for producing a toner for developing an electrostatic charge image includes a resin particle / release agent for preparing a resin particle / release agent mixed dispersion in which resin particles containing a resin and a release agent are melt-mixed and dispersed. Mixing step of mixing agent dispersion, mixing resin particle / release agent mixture dispersion and colorant dispersion in which colorant is dispersed to form agglomerated particles, and fusing the aggregated particles by heating It is preferable that the method includes a process. By this method, there are advantages such that it is easy to produce a small-diameter toner and release agent particles are easily included.

  Hereafter, each process in an example of the manufacturing method of the electrostatic image developing toner will be described in detail. The toner manufacturing method according to the present embodiment is not limited to this.

[Dispersion preparation process]
In the dispersion preparation step, a resin particle dispersion, a colorant dispersion, a release agent dispersion, a resin particle / release agent mixed dispersion, and the like are prepared.

  The resin particle dispersion may be prepared by using a known phase inversion emulsification method or a method in which the resin particle dispersion is heated to a temperature higher than the glass transition temperature of the resin and emulsified by mechanical shearing force. At this time, an ionic surfactant may be added.

  The colorant dispersion may be prepared by dispersing colorant particles of a desired color such as yellow, cyan, magenta, and black in a solvent using, for example, an ionic surfactant.

  The release agent dispersion is, for example, a release agent dispersed in water together with a polymer electrolyte (for example, an ionic surfactant, a polymer acid, a polymer base, etc.), and heated above the melting point of the release agent. At the same time, the particle size may be adjusted with a homogenizer or a pressure discharge type disperser that can be subjected to strong shearing.

  The resin particle / release agent mixed dispersion is obtained by, for example, melting and kneading a resin and a release agent in advance by dry or wet method, adding the kneaded material in water, and heating it to a temperature higher than the glass transition temperature of the resin. What is necessary is just to prepare by the method of emulsifying with a shearing force etc.

[Aggregation process]
In the aggregation process, the resin particle dispersion, the colorant dispersion, and the release agent dispersion are mixed, and the resin particles, the release agent, and, if necessary, the colorant are hetero-aggregated to obtain a desired toner diameter. Aggregated particles (core aggregated particles) having a close diameter are formed. Alternatively, the resin particle / release agent mixed dispersion and the colorant dispersion are mixed, and the resin particles, the release agent and, if necessary, the colorant are hetero-aggregated to have a diameter substantially close to the desired toner diameter. Aggregated particles (core aggregated particles) are formed.

[Shell layer forming step]
In the shell layer forming step, the resin particles are adhered to the surface of the core aggregated particles using a resin particle dispersion containing resin particles to form a coating layer (shell layer) having a desired thickness, thereby forming the core aggregated particles. Agglomerated particles having a core / shell structure with a shell layer formed on the surface (core / shell agglomerated particles) are obtained.

  In addition, the aggregation process and the shell layer forming process may be repeatedly performed in a plurality of stages.

  Here, the volume average particle diameter of the resin particles, the colorant, and the release agent used in the aggregation process and the shell layer forming process is to easily adjust the toner diameter and the particle size distribution to desired values. It is preferably 1 μm or less, and more preferably in the range of 100 nm to 300 nm.

  The volume average particle diameter is measured using a laser diffraction particle size distribution measuring apparatus (LA-700: manufactured by Horiba Seisakusho). As a measuring method, the sample in the state of dispersion is adjusted so as to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 mL. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the place where the accumulation reaches 50% is defined as the volume average particle diameter.

[Stop process]
In the stopping step, the aggregation growth of the aggregated particles is stopped by adjusting the pH in the aggregation system. Specifically, the growth of the aggregated particles is stopped by adjusting the pH in the aggregated system to a range of 6 to 9.

[Fusion process]
In the fusing step (fusing / unifying step), first, resin particles contained in the agglomerated particles in a solution containing the agglomerated particles obtained through the agglomeration step and the shell formation step performed as necessary. The toner particles are obtained by fusing and coalescing by heating to a temperature equal to or higher than the melting point or glass transition temperature.

[Washing process]
In the washing step, the dispersion of toner particles obtained in the fusion step is at least subjected to substitution washing with ion-exchanged water to perform solid-liquid separation. The solid-liquid separation method is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity.

[Drying process]
In the drying step, the wet cake that has been subjected to solid-liquid separation is dried to obtain toner particles. The drying method is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used from the viewpoint of productivity.

<Physical properties of toner for developing electrostatic image>
The volume average particle diameter of the electrostatic image developing toner according to this embodiment is preferably in the range of 4 μm to 8 μm, more preferably in the range of 5 μm to 7 μm, and the number average particle diameter is 3 μm to 7 μm. The following range is preferable, and the range of 4 μm or more and 6 μm or less is more preferable.

  The volume average particle diameter and the number average particle diameter are measured by measuring with an aperture diameter of 100 μm using a Coulter Multisizer II type (manufactured by Beckman-Coulter). At this time, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds.

  The volume average particle size distribution index GSDv of the electrostatic image developing toner according to this embodiment is 1.27 or less, preferably 1.25 or less. When GSDv exceeds 1.27, the particle size distribution is not sharp, resolution is deteriorated, and image defects such as toner scattering and fogging may be caused.

The volume average particle diameter D50v and the volume average particle size distribution index GSDv are obtained as follows. Draw a cumulative distribution from the small diameter side for the volume and number of the particle size range (channel) divided based on the particle size distribution of the toner measured by the above-mentioned Coulter Multisizer II (manufactured by Beckman-Coulter). In addition, the particle diameter that is accumulated 16% is defined as volume D16v and several D16p, the particle diameter that is accumulated 50% is defined as volume D50v and several D50p, and the particle diameter that is accumulated 84% is defined as volume D84v and several D84p. At this time, D50v represents the volume average particle diameter, and the volume average particle size distribution index (GSDv) is determined as (D84v / D16v) ^1/2 . In addition, (D84p / D16p) ^1/2 represents a number average particle size distribution index (GSDp).

In addition, the shape factor SF1 represented by the following formula of the toner for developing an electrostatic charge image according to the exemplary embodiment is preferably in the range of 110 to 140, more preferably in the range of 115 to 130.
SF1 = (ML ² / A) × (π / 4) × 100
[In the above formula, ML represents the maximum toner length (μm), and A represents the projected area (μm ² ) of the toner. ]
When the toner shape factor SF1 is smaller than 110 or exceeds 140, excellent chargeability, cleaning properties, and transferability may not be obtained over a long period of time.

The shape factor SF1 is measured as follows using a Luzex image analyzer (FT manufactured by Nireco Corporation). First, an optical microscopic image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length (ML) and projection area (A) of 50 toners are measured. ML ² / A) × (π / 4) × 100 is calculated, and a value obtained by averaging is calculated as the shape factor SF1.

<Developer for developing electrostatic image>
In this embodiment, the developer for developing an electrostatic charge image is not particularly limited except that it contains the toner for developing an electrostatic charge image of the present embodiment, and may have an appropriate component composition depending on the purpose. The electrostatic charge image developing developer in the present embodiment is a one-component electrostatic charge image developing developer when the electrostatic charge image developing toner is used alone, or a two-component developer when used in combination with a carrier. It becomes a developer for developing an electrostatic image.

  For example, in the case of using a carrier, the carrier is not particularly limited, and examples thereof include known carriers. For example, resins described in JP-A Nos. 62-39879 and 56-11461 are disclosed. Known carriers such as a coated carrier can be used.

  Specific examples of the carrier include the following resin-coated carriers. Examples of the core particles of the carrier include normal iron powder, ferrite, and magnetite molding, and the volume average particle size is in the range of about 30 μm to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl Homopolymers such as vinyl ketones such as ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene; and copolymers composed of two or more types of monomers Furthermore, silicone resins containing methyl silicone, methyl phenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like can be mentioned. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by weight and more preferably in the range of 0.5 to 3.0 parts by weight with respect to 100 parts by weight of the core particles. preferable.

  For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer or the like may be used. Depending on the amount of the coating resin, a heating type fluidized rolling bed, a heating type kiln or the like may be used.

  The mixing ratio of the electrostatic image developing toner of the present embodiment and the carrier in the developer for developing an electrostatic image is not particularly limited and may be appropriately selected according to the purpose.

<Toner cartridge>
The toner cartridge according to the present embodiment is not particularly limited as long as it contains the electrostatic image developing toner of the present embodiment. For example, the toner cartridge is attached to and detached from an image forming apparatus including a developing unit, and contains the toner for developing an electrostatic charge image of the present embodiment as toner to be supplied to the developing unit.

<Process cartridge>
The process cartridge according to the present embodiment includes an image carrier and developing means for developing a latent electrostatic image formed on the surface of the image carrier using a developer to form a toner image. The process cartridge according to the present embodiment includes a charging unit for charging the surface of the image holding member, a charging member cleaning member for cleaning the charging member, and a latent image on the surface of the charged image holding member, as necessary. A latent image forming unit that forms a toner image, a transfer unit that transfers a toner image formed on the surface of the image carrier to a transfer target, and a residual toner removal that removes residual toner remaining on the surface of the image carrier after transfer You may provide at least 1 type selected from the group which consists of means.

  A schematic configuration of an example of a process cartridge according to an embodiment of the present invention is shown in FIG. 1, and the configuration will be described. The process cartridge 1 includes a photoconductor (electrophotographic photoconductor) 10 as an image carrier on which an electrostatic latent image is formed, a cylindrical charging roll 12 as a charging member that contacts and charges the surface of the photoconductor 10, A toner image is formed by adhering toner to a cleaning roll 14 as a charging member cleaning member that contacts the charging roll 12 to clean the surface of the charging roll 12 and an electrostatic latent image formed on the surface of the photoreceptor 10. A developing roller 16 as a developing unit and a cleaning blade 20 as a residual toner removing unit that contacts the surface of the photoconductor 10 and removes residual toner remaining on the surface of the photoconductor 10 after transfer are integrally supported. It is detachable from the image forming apparatus. When mounted on the image forming apparatus, an exposure device 22 as a latent image forming unit that forms an electrostatic latent image on the surface of the photoconductor 10 around the photoconductor 10 by a charging roll 12, laser light, or reflected light of a document. The developing roll 16, the transfer roll 18 serving as transfer means for transferring the toner image on the surface of the photoconductor 10 onto the recording paper 26 as the transfer target, and the cleaning blade 20 are arranged in this order. In FIG. 1, description of functional units normally required in other electrophotographic processes is omitted.

  The operation of the process cartridge 1 according to this embodiment will be described.

  First, the surface of the photoconductor 10 is uniformly charged to a high potential by supplying a voltage from a high voltage power source (not shown) to the charging roll 12 in contact with the surface of the photoconductor 10. At this time, the photoconductor 10 and the charging roll 12 rotate in the directions of arrows in FIG. After charging, when image light (exposure) corresponding to image information is irradiated onto the surface of the photoconductor 10 by the exposure device 22, the potential of the irradiated portion decreases. Since the image light has a light amount distribution corresponding to the black / white of the image, a potential distribution corresponding to the recorded image, that is, an electrostatic latent image is formed on the surface of the photoconductor 10 by irradiation of the image light. When the portion where the electrostatic latent image is formed passes through the developing roll 16, toner adheres according to the level of the potential, and a toner image in which the electrostatic latent image is visualized is formed. The recording paper 26 is conveyed to a portion where the toner image is formed by a resist roll (not shown) at a predetermined timing, and overlaps the toner image on the surface of the photoreceptor 10. After the toner image is transferred to the recording paper 26 by the transfer roll 18, the recording paper 26 is separated from the photoreceptor 10. The separated recording paper 26 is transported through a transport path, fixed by heating and pressure by a fixing unit (not shown) as fixing means, and then discharged outside the apparatus.

  A cleaning roll 14 is installed on the charging roll 12 provided in the process cartridge 1, and a voltage is applied to the bearing from a high-voltage power supply, and the cleaning roll 14 has the same polarity as the charging roll 12, thereby cleaning foreign matter. Since it moves with little accumulation on the surfaces of the roll 14 and the charging roll 12 and is collected by the cleaning blade 20, foreign matters such as toner adhering to the charging member are stably removed over a long period of time. For this reason, a stable charging performance is maintained with little accumulation of dirt on the charging roll 12 over a long period of time.

  The photoreceptor 10 has a function of forming at least an electrostatic latent image (electrostatic charge image). In the electrophotographic photosensitive member, an undercoat layer, a charge generation layer containing a charge generation material, and a charge transport layer containing a charge transport material are formed in this order on the outer peripheral surface of a cylindrical conductive substrate as necessary. It is a thing. The order of stacking the charge generation layer and the charge transport layer may be reversed. These are laminated photoconductors in which a charge generation material and a charge transport material are contained in separate layers (charge generation layer, charge transport layer), but both the charge generation material and the charge transport material are the same. A single-layer type photoreceptor included in the above layer may be used, and a laminated photoreceptor is preferable. Further, an intermediate layer may be provided between the undercoat layer and the photosensitive layer. Further, a protective layer may be provided on the photosensitive layer. In addition, other types of photosensitive layers such as an amorphous silicon photosensitive film may be used in addition to the organic photoreceptor.

  The exposure device 22 is not particularly limited. For example, a laser optical system that exposes a light source such as semiconductor laser light, LED light, or liquid crystal shutter light on the surface of the photoconductor 10 in a desired image-like manner, or an optical such as an LED array. System equipment.

  The developing unit has a function of developing the electrostatic latent image formed on the photoreceptor 10 with a one-component developer or a two-component developer containing an electrostatic charge image developing toner to form a toner image. Such a developing device is not particularly limited as long as it has the above-described function, and may be appropriately selected according to the purpose. It may be a thing. For example, as shown in FIG. 1, a developing device having a function of attaching toner for developing an electrostatic charge image to the photoreceptor 10 using the developing roll 16, or development having a function of attaching the toner to the photoreceptor 10 using a brush or the like. And a known developing device.

  The transfer unit may be a type that directly transfers to paper or the like, or a type that transfers via an intermediate transfer member. For example, a transfer roll 18 and a transfer roll pressing device (not shown) using a conductive or semiconductive roll that directly transfers through a recording sheet 26 as shown in FIG. 1 may be used. Alternatively, a recording paper 26 may be used in which a charge opposite in polarity to the toner is applied to the recording paper 26 from the back side of the recording paper 26 (opposite to the photoreceptor) and the toner image is transferred to the recording paper 26 by electrostatic force. The transfer roll 18 may be arbitrarily set depending on the width of the image area to be charged, the shape of the transfer charger, the opening width, the process speed (circumferential speed), and the like. Further, a single layer foam roll or the like is preferably used as the transfer roll 18 for cost reduction.

  The fixing unit as the fixing unit is not particularly limited as long as the toner image transferred onto the recording paper 26 is fixed by heating, pressing, or heating and pressing. For example, a fixing device including a heating roll and a pressure roll is used.

  Examples of the recording paper 26 that is a transfer target to which the toner image is transferred include plain paper, an OHP sheet, and the like used in electrophotographic copying machines and printers. In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer material is as smooth as possible. Preferably used.

  The recording paper 26 is not limited to plain paper having a surface roughness of 2.0 μm or more and 3.5 μm or less, or coated paper of 0.5 μm or more and 1.9 μm or less. The occurrence of uneven gloss is suppressed.

<Image forming apparatus>
The image forming apparatus according to the present embodiment includes an image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, and a developer that develops the electrostatic latent image formed on the surface of the image carrier. And developing means for forming a toner image by developing the toner image, and transfer means for transferring the developed toner image to a transfer target. The image forming apparatus according to the present exemplary embodiment fixes a charging member that charges the surface of the image holding member, a charging member cleaning member for cleaning the charging member, and a toner image transferred to the transfer target, as necessary. Fixing means for removing the toner, residual toner removing means for removing residual toner remaining on the surface of the image carrier after transfer, and collecting the residual toner removed by the residual toner removing means, and developing the collected residual toner There may be provided at least one selected from the group consisting of a residual toner collecting and supplying means for supplying to the means. The image forming apparatus according to the present embodiment may use the process cartridge.

  FIG. 2 shows a schematic configuration of an example of the image forming apparatus according to the present embodiment, and the configuration will be described. The image forming apparatus 3 includes a photoconductor 10 as an image carrier on which an electrostatic latent image is formed, a cylindrical charging roll 12 as a charging member that contacts and charges the surface of the photoconductor 10, and a contact with the charging roll 12. Then, a cleaning roll 14 as a charging member cleaning member for cleaning the surface of the charging roll 12 and exposure as a latent image forming means for forming an electrostatic latent image on the surface of the photosensitive member 10 by laser light or reflected light of the original. The apparatus 22, a developing roll 16 as a developing unit that forms a toner image by attaching toner to the electrostatic latent image formed on the surface of the photoconductor 10, and the toner image on the surface of the photoconductor 10 are the transfer target. A transfer roll 18 serving as a transfer unit that performs transfer processing on the recording paper 26 and a residual toner removing unit that contacts the surface of the photoconductor 10 to remove residual toner remaining on the surface of the photoconductor 10 after transfer. And a cleaning blade 20 of and. In the image forming apparatus 3, a charging roll 12, an exposure device 22, a developing roll 16, a transfer roll 18, and a cleaning blade 20 are arranged around the photoreceptor 10 in this order. Further, a fixing device 28 including a heating roll 30 and a pressure roll 32 is provided as fixing means. In FIG. 2, functional units normally required in other electrophotographic processes are omitted. Each configuration of the image forming apparatus 3 and the operation during image formation are the same as those of the process cartridge 1 of FIG.

  In the image forming apparatus according to the present embodiment, the transfer target on which an unfixed image is formed is passed between a heating member such as the heating roll 30 and a pressure member such as the pressure roll 32. The thermal conductivity of the surface layer is preferably 1 W / m · K or more. When using a fixing roll with high thermal conductivity, the temperature unevenness given to the unfixed image is large and the releasability is also insufficient, so uneven adhesion is likely to occur, which may have effects such as uneven luster and plain pattern. . Even when an image is formed on a sheet having a large surface irregularity in an image forming apparatus using a fixing roll excellent in energy saving using a fixing roll having a high thermal conductivity with little heat loss by using the toner according to the present embodiment. The occurrence of uneven gloss is suppressed.

  The respective configurations of the image forming apparatus according to the present embodiment are not limited to these, and conventionally known configurations may be applied as the respective configurations of the electrophotographic image forming apparatus. That is, the charging member, charging member cleaning unit, latent image forming unit, developing unit, transfer unit, residual toner removing unit, residual toner collecting and supplying unit, static eliminating unit, paper feeding unit, conveying unit, image control unit, etc. are necessary. Accordingly, conventionally known ones are appropriately employed. These configurations are not particularly limited in the present embodiment.

  Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.

[Preparation of crystalline resin 1]
By mixing in a flask at a ratio of 54 mol% of hexanediol, 46 mol% of dodecanedioic acid and 0.1 mol% of dibutyltin oxide as a catalyst, heating to 220 ° C. in a reduced pressure atmosphere, and conducting a dehydration condensation reaction for 6 hours, A functional polyester resin was obtained. GPC measurement was performed under the following conditions to obtain a crystalline resin having a weight average molecular weight of 45,000.

(GPC measurement)
A measuring instrument “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” was used, and two columns of “TSKgel, SuperHM-H (manufactured by Tosoh Corporation, 6.0 mm ID × 15 cm)” were used. , THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

[Preparation of Amorphous Resin 1]
In a reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, dimethyl terephthalate 23 mol%, isophthalic acid 10 mol%, dodecenyl succinic anhydride 15 mol%, trimellitic anhydride 3 mol%, bisphenol A ethylene oxide The adduct was added at a ratio of 5 mol% and bisphenol A propylene oxide adduct 45 mol%, and the reaction vessel was replaced with dry nitrogen gas, and then added as a catalyst at a ratio of 0.06 mol% of dibutyltin oxide, and about 190 in a nitrogen gas stream. Stirring reaction is carried out at 7 ° C for about 7 hours, the temperature is further raised to about 250 ° C and stirring reaction is carried out for about 5.0 hours, and then the reaction vessel is depressurized to 10.0 mmHg and stirred for about 0.5 hours under reduced pressure. To obtain a polyester resin. The weight average molecular weight Mw of the polyester resin was 90,000, and the number average molecular weight Mn was 15,000.

[Preparation of crystalline resin / release agent mixed dispersion 1]
Using crystalline resin 1 and carnauba wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 12 ° C.), crystalline resin 40 parts by mass, carnauba wax 40 parts by mass and 720 parts by weight of deionized water was placed in a stainless steel beaker, heated to 90 ° C. in a warm bath, and when the crystalline polyester resin and wax mixture melted, using a homogenizer (manufactured by IKA: Ultra Turrax T50). Stir at 10,000 rpm. Next, the emulsion was dispersed while adding 1.8 parts by mass of an anionic surfactant (manufactured by Kao: Latemul PSK; 20% by mass), and a crystalline resin / release agent dispersion (1) having an average particle size of 0.160 μm. (Solid content 10% by mass, resin particle concentration 5% by mass, release agent concentration 5% by mass).

[Preparation of crystalline resin / release agent mixed dispersion 2]
Crystalline resin / release agent mixed dispersion 1 except that purified wax wax (acid value 6 mgKOH / g, endothermic peak temperature 50 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 12 ° C.) was used as the release agent. In the same manner as described above, a crystalline resin / release agent mixed dispersion 2 (release agent concentration: 5 mass%) having a volume average particle size of 0.170 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 3]
Crystalline resin / release agent mixed dispersion except that purified candelilla wax (acid value 6 mgKOH / g, endothermic peak temperature 80 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 13 ° C.) was used as the release agent. In the same manner as in Example 1, a crystalline resin / release agent mixed dispersion 3 (release agent concentration: 5 mass%) having a volume average particle size of 0.145 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 4]
Crystalline resin / release agent mixed dispersion 1 except that purified rice wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 10 ° C., peak temperature difference 11 ° C.) was used as the release agent. In the same manner as described above, a crystalline resin / release agent mixed dispersion 4 (release agent concentration: 5 mass%) having a volume average particle size of 0.15 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 5]
Crystalline resin / release agent mixed dispersion 1 except that purified ester wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 20 ° C., peak temperature difference 14 ° C.) was used as the release agent. In the same manner as above, a crystalline resin / release agent mixed dispersion 5 having a volume average particle size of 0.22 μm (release agent concentration: 5 mass%) was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 6]
A crystalline resin / release agent mixed dispersion 1 except that paraffin wax (acid value 3 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 15 ° C.) was used as a release agent. Similarly, a crystalline resin / release agent mixed dispersion 6 (release agent concentration: 5 mass%) having a volume average particle size of 0.18 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 7]
Crystalline resin / release agent mixed dispersion 1 except that purified beeswax wax (acid value 10 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 10 ° C.) was used as the release agent. In the same manner as described above, a release agent dispersion liquid 7 (crystalline resin / release agent concentration: 5 mass%) having a volume average particle size of 0.165 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 8]
Crystalline resin / release agent, except that ethylene glycol monohydroxystearate wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 5 ° C.) was used as the release agent. In the same manner as in the mixed dispersion 1, a crystalline resin / release agent mixed dispersion 8 having a volume average particle size of 0.16 μm (release agent concentration: 5 mass%) was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 9]
Crystalline resin / release agent mixed dispersion except that stearyl hydroxystearate wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 20 ° C.) was used as a release agent. In the same manner as Liquid 1, a crystalline resin / release agent mixed dispersion 9 (release agent concentration: 5% by mass) having a volume average particle size of 0.2 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 10]
Crystalline resin / release agent, except that hydroxystearic acid ester wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 4.8 ° C.) was used as the release agent. In the same manner as in the mixed dispersion 1, a crystalline resin / release agent mixed dispersion 10 (release agent concentration: 5% by mass) having a volume average particle size of 0.18 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 11]
Crystalline resin / release agent mixed dispersion except that acid value polyethylene wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 21 ° C.) was used as the release agent. In the same manner as in Example 1, a crystalline resin / release agent mixed dispersion 11 (release agent concentration: 5 mass%) having a volume average particle size of 0.20 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 12]
Crystalline resin / release agent mixed dispersion except that glycerin monooleate wax (acid value 6 mgKOH / g, endothermic peak temperature 42 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 13 ° C.) was used as a release agent. In the same manner as in Example 1, a crystalline resin / release agent mixed dispersion 12 having a volume average particle size of 0.18 μm (release agent concentration: 5 mass%) was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 13]
A crystalline resin / release, except that montan wax (Licowax E acid-end modified acid value 6 mg KOH / g, endothermic peak temperature 83 ° C., 10% endothermic temperature range 15 ° C., peak temperature difference 14.5 ° C.) was used as a release agent. A crystalline resin / release agent mixed dispersion 13 (release agent concentration: 5% by mass) having a volume average particle size of 0.25 μm was prepared in the same manner as in the release agent mixture dispersion 1.

[Preparation of crystalline resin / release agent mixed dispersion 14]
Crystalline resin / release agent, except that glycerin monostearate wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 8 ° C., peak temperature difference 12.5 ° C.) was used as the release agent. In the same manner as the mixed dispersion 1, a crystalline resin / release agent mixed dispersion 14 (release agent concentration: 5% by mass) having a volume average particle size of 0.18 μm was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 15]
Crystalline resin / release agent mixed dispersion except that montan wax (Licowax KST acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 22 ° C., peak temperature difference 13 ° C.) was used as the release agent. In the same manner as in Example 1, a crystalline resin / release agent mixed dispersion 15 having a volume average particle size of 0.21 μm (release agent concentration: 5 mass%) was prepared.

[Preparation of crystalline resin / release agent mixed dispersion 16]
Crystalline resin / release, except that ester wax (Wep3, NOF acid value 1.0 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature range 15 ° C., peak temperature difference 13 ° C.) was used as the release agent. In the same manner as in the agent mixture dispersion 1, a crystalline resin / release agent mixture dispersion 16 (release agent concentration: 5% by mass) having a volume average particle size of 0.19 μm was prepared.

[Preparation of Crystalline Resin / Releasing Agent Mixture Dispersion 17]
Crystalline resin / release agent mixed dispersion except that unrefined candelilla wax (acid value 12 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 12 ° C.) was used as a release agent. In the same manner as Liquid 1, a release agent dispersion liquid 17 (crystalline resin / release agent concentration: 5 mass%) having a volume average particle size of 0.18 μm was prepared.

[Preparation of crystalline resin dispersion 1]
When 40 parts by mass of crystalline resin 1 and 760 parts by mass of deionized water are placed in a stainless steel beaker and heated to 90 ° C. in a warm bath, when the crystalline resin is melted, a homogenizer (manufactured by IKA: Ultra Turrax) The mixture was stirred at 10,000 rpm using T50). Next, the emulsion was dispersed while adding 1.8 parts by mass of an anionic surfactant (manufactured by Kao: Latemulu PS; 20% by mass) to obtain a crystalline resin dispersion (1) (solid content) having an average particle size of 0.180 μm. 5 mass%, resin particle concentration 5 mass%).

[Preparation of release agent dispersion 1]
Carnauba wax (acid value 6 mg KOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature range 15 ° C., peak temperature difference 12 ° C.) 40 parts by mass and deionized water 760 parts by mass in a stainless steel beaker, warm bath Then, after heating to 90 ° C., when the crystalline resin was melted, the mixture was stirred at 10,000 rpm using a homogenizer (manufactured by IKA: Ultra Tarrax T50). Next, while 1.8 parts by mass of an anionic surfactant (manufactured by Kao: Latemul PS; 20% by mass) was added dropwise, emulsification and dispersion were performed, and a release agent dispersion (1) (solid content having an average particle size of 0.175 μm) 5 mass%, resin particle concentration 5 mass%).

[Preparation of Amorphous Resin / Releasing Agent Mixture Dispersion 1]
Using amorphous resin 1 and carnauba wax (acid value 6 mgKOH / g, endothermic peak temperature 65 ° C., 10% endothermic temperature width 15 ° C., peak temperature difference 14.5 ° C.), crystalline resin / release agent mixed dispersion An amorphous resin / release agent mixed dispersion having a volume average particle size of 0.25 μm (resin particle concentration: 5 mass%, release agent concentration: 5 mass) in the same manner as the method and conditions shown in Liquid 1. %) Were prepared simultaneously.

[Preparation of colorant dispersion]
Cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)) 1,000 parts by weight Anionic surfactant (Kao, Perex NBL 20% by weight) 150 parts by weight Deionized water 4,000 parts by weight A colorant dispersion obtained by mixing and dissolving the above and dispersing the colorant (cyan pigment) by dispersing for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). Prepared. The volume average particle size of the colorant (cyan pigment) in the colorant dispersion was 0.15 μm, and the colorant particle concentration was 20% by mass.

[Preparation of inorganic fine particle dispersion 1]
Titanium oxide fine particles (Sakai Chemical STR-60C-LP) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 5 parts by weight Ion-exchanged water 200 parts by weight The above is mixed and homogenizer (manufactured by IKA) Inorganic fine particle dispersion containing titanium fine particles having a volume average particle size of 0.4 μm after being dispersed for 10 minutes using Ultra Turrax T50), and then subjected to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP). 1 was obtained.

[Manufacture of Fixing Roll 1]
The surface of an aluminum pipe (metal cylinder) with a diameter of 35 mm and a thickness of 2.0 mm was subjected to electroless plating with an electroless nickel plating bath (trade name “Kanizen”, manufactured by Nihon Kanigen) to form a plating film having a nickel thickness of 10 μm. . Thereafter, the aluminum pipe was put into a badge furnace, and heat treatment was performed at 400 ° C. for 30 minutes, whereby the phosphoric acid component and the surfactant in the plating film were decomposed to form a hard plating film. The thermal conductivity of the surface layer of the fixing roll was measured by the following method and found to be 10 W / m · K.

[Manufacture of Fixing Roll 2]
Electroless plating is performed on the surface of an aluminum pipe (metal cylinder) with a diameter of 35 mm and a thickness of 2.0 mm using an electroless nickel plating bath (trade name “Kaniflon A”, manufactured by Nihon Kanisen) in which PTFE particles are dispersed in advance. A plating film having a thickness of 50 μm formed of nickel and PTFE particles was formed. Thereafter, the aluminum pipe was put into a badge furnace, and heat treatment was performed at 400 ° C. for 30 minutes, whereby the phosphoric acid component and the surfactant in the plating film were decomposed to form a hard plating film. The thermal conductivity of the surface layer of the fixing roll 2 was 1.5 W / m · K.

[Manufacture of Fixing Roll 3]
The surface of an aluminum pipe with a diameter of 35 mm and a thickness of 2.0 mm is subjected to pretreatment such as surface cleaning and primer coating, followed by powder coating with a PFA resin powder coating (trade name MP-10, manufactured by DuPont) and firing. The process and the circumferential polishing process were repeated to form a fluororesin layer having a surface roughness Rz = 2.0 μm and a thickness of 20 μm. The thermal conductivity of the surface layer of the fixing roll 3 was 0.8 W / m · K.

[Method for measuring thermal conductivity of fixing roll surface layer]
The thermal conductivity of the outermost layer of the heating member in the present example is measured using a commercially available thermal conductivity measuring instrument (for example, NC074 series manufactured by Eikoku Seiki Co., Ltd., rapid thermal conductivity meter M69M-500 manufactured by Shiro Sangyo Co., Ltd., etc.). It was measured.

<Example 1>
[Preparation of toner particles]
Crystalline resin / release agent mixed dispersion 300 parts by weight Colorant dispersion 50 parts by weight Release agent dispersion 60 parts by weight Aluminum sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) 0.5 part by weight Surfactant aqueous solution (Perex NBL ( 35% active ingredient), sodium alkyl naphthalene sulfonate, manufactured by Kao Corporation) 65 parts by weight ion-exchanged water 300 parts by weight The above ingredients are contained in a round stainless steel flask and homogenizer (manufactured by IKA, Ultrata). After dispersion using Lux T50), the mixture was heated to 45 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C., it was confirmed that aggregated particles having an average particle diameter of about 5.2 μm or more were formed. Subsequently, 15 parts by mass of a 1N aqueous sodium hydroxide solution was gently added to adjust the pH to 7.5, and then the mixture was heated to 90 ° C. while stirring was continued for 3 hours. Thereafter, the reaction product was filtered, sufficiently washed with ion exchange water, and then dried using a vacuum dryer to obtain toner particles.

[Toner Preparation]
1 part by mass of acicular rutile-type titanium oxide (volume average particle diameter D50: 15 nm, powder resistance: 10 ¹⁵ Ωcm) surface-treated with decylsilane as an additive with respect to 100 parts by mass of toner particles, using a Henschel mixer Then, coarse particles were removed using a 45 μm mesh sieve to obtain a toner.

[Developer preparation]
Ferrite particles (volume average particle size: 50 μm) 100 parts by mass Toluene 14 parts by mass Styrene-methacrylate copolymer (component ratio: 90/10, weight average molecular weight: 70,000)
2 parts by mass Carbon black (R330: manufactured by Cabot Corporation) 0.2 parts by mass First, the above components except for ferrite particles are stirred with a stirrer for 10 minutes to prepare a dispersed coating resin solution, and then this coating resin The liquid and the ferrite particles are placed in a vacuum degassing kneader, stirred at 60 ° C. for 30 minutes, further depressurized while warming, degassed, and dried to obtain a carrier. The mixture was stirred and mixed with 10 parts by mass of toner and 200 parts by mass of carrier, and a developer was obtained using a sieve having a mesh size of 212 μm.

[Measurement method of storage elastic modulus G ′ (100) at 100 ° C. and storage elastic modulus G ′ (200) at 200 ° C. in toner frequency 6.28 Rad dynamic viscoelasticity measurement]
The storage elastic modulus G ′ and the loss elastic modulus G ″ were measured using a rheometer (Rheometric Scientific: ARES rheometer) and using a parallel plate at a frequency of 6.28 Rad. . After the sample set is cooled to room temperature at about 120 ° C. to 140 ° C., it is heated at a rate of temperature increase of 1 ° C./min, and the storage elastic modulus G ′, loss elastic modulus G ″ at the time of temperature increase every 1 ° C., and Tan δ was measured.

[Differential thermal analysis of release agent in toner]
Furthermore, the DSC measurement was performed based on ASTM D3418-8 using a conventionally known differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC60A). The temperature of the detection part of the apparatus was corrected using the melting points of indium and zinc, and the heat quantity was corrected using the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min. The temperature is raised from room temperature (10 ° C to 30 ° C) to 150 ° C for the first time, cooled to 0 ° C at 10 ° C / min, and then again heated to 150 ° C at 10 ° C / min for the second time. The temperature range of the endothermic peak temperature, exothermic peak temperature, and endothermic peak temperature of the release agent in the second measurement result was calculated from the baseline at the endothermic peak at a height of 10% of the peak height and parallel to the baseline.

[Method for Measuring Acid Value of Release Agent in Toner]
The acid value of the release agent in the toner was measured by the potentiometric titration method of JIS K0070-1992.

[Evaluation of uneven gloss]
Using developer 1 and fixing roll 1, gloss unevenness was evaluated using a modified machine of a color copying machine “DocuCentre-II C7500” manufactured by Fuji Xerox Co., Ltd. Evaluation was made after each developer was added, using high-temperature and high-humidity environment (32 ° C./90% RH), SP paper (Fuji Xerox Office Supply, basis weight 64 g / m ² ), continuous 10,000 sheets Was printed. As the printed image, an image was used in which a band having a sheet width of 50% perpendicular to the process direction and an image density of 2% was formed at a position 50 mm from the leading end of the sheet. After printing 10,000 sheets, collect 10 solid images on paper (Dao Paper Co., Ltd. A4 size) so that the image density is 1.3 to 1.5 (measured with X-Rite 404), gloss unevenness Was evaluated by visual confirmation. Evaluation was performed according to the following criteria. The results are shown in Table 1.
◎: Good unevenness cannot be confirmed, but very good ○: Unevenness can be barely confirmed in solid parts of 1 or more and 2 places or less Good △: Unevenness is barely confirmed in solid parts of 3 or more and 4 places or less, but actual use No problem ×: Unevenness is confirmed in 5 or more solid parts

[Stress feed test evaluation]
Create a solid image on cardboard (basis weight 200g / m ² ) using the modified color copier described above (density 1.5 to 1.7), and set 20 sheets on the automatic current feeder. The test of running automatically was repeated 5 times, and the shading unevenness of the solid part on the image was visually evaluated. Evaluation was performed according to the following criteria. The results are shown in Table 1.
◎: Image disorder, no defects, very good ○: Out of 20 images, 1 to 2 images are very slightly distorted, but △: Out of 20 images, 3 to 4 images are very slightly distorted No problem in actual use ×: Image sag or defect that can be clearly seen with 5 or more images

<Example 2>
Toner particles 2, toner 2 and developer 2 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 2 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
Toner particles 3, toner 3 and developer 3 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 3 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
Toner particles 4, toner 4 and developer 4 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 4 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 5>
Toner particles 5, toner 5 and developer 5 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 5 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 6>
Toner particles 6, toner 6 and developer 6 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 6 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 7>
Toner particles 7, toner 7 and developer 7 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 7 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 8>
Toner particles 8, toner 8 and developer 8 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 8 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 9>
Toner particles 9, toner 9 and developer 9 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 9 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 10>
Toner particles 10, toner 10 and developer 10 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 10 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 11>
Toner particles 11, toner 11 and developer 11 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 11 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 12>
In the same manner as in Example 1 except that the crystalline resin dispersion 1 and the release agent dispersion 1 were used in place of the crystalline resin / release agent mixed dispersion 1, toner particles 12, toner 12, and developer were used. 12 was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 13>
In the same manner as in Example 1, except that the amorphous resin / release agent mixed dispersion 1 was used instead of the crystalline resin / release agent mixed dispersion 1, toner particles 13, toner 13 and developer 13 were used. Was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 14>
In the same manner as in Example 1 except that the crystalline resin / release agent mixed dispersion 12 was used in place of the crystalline resin / release agent mixed dispersion 1, toner particles 14, toner 14 and developer 14 were removed. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 15>
In the same manner as in Example 1 except that the crystalline resin / release agent mixed dispersion 13 was used instead of the crystalline resin / release agent mixed dispersion 1, toner particles 15, toner 15 and developer 15 were removed. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 16>
Toner particles 16, toner 16 and developer 16 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 14 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 17>
In the same manner as in Example 1 except that the crystalline resin / release agent mixed dispersion 15 was used instead of the crystalline resin / release agent mixed dispersion 1, toner particles 17, toner 17 and developer 17 were removed. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 18>
Toner particles 18, toner 18 and developer 18 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 16 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 19>
Toner particles 19, toner 19 and developer 19 were prepared in the same manner as in Example 1 except that crystalline resin / release agent mixed dispersion 17 was used instead of crystalline resin / release agent mixed dispersion 1. Prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 20>
Toner particles 20, toner 20, developer by the same method as in Example 1 except that 10 parts by weight of the titanium oxide fine particle dispersion and 50 parts by weight of 1% aqueous solution of calcium chloride dihydrate instead of aluminum sulfate were used. 20 were prepared and evaluated. The results are shown in Table 1.

<Example 21>
When preparing toner particles, 1N sodium hydroxide was added until the pH reached 9.0, followed by 20 parts by weight of Clewat OH300 (hydroxyethylethylenediaminetriacetic acid, 10% diluted solution manufactured by Nagase Chemtech) as an ion sequestering agent. A toner particle 21, toner 21 and developer 21 were prepared and evaluated in the same manner as in Example 1 except that. The results are shown in Table 1.

<Example 22>
Evaluation was performed in the same manner as in Example 1 except that the fixing roll 2 was used instead of the fixing roll 1. The results are shown in Table 1.

<Example 23>
Evaluation was performed in the same manner as in Example 1 except that the fixing roll 3 was used instead of the fixing roll 1. The results are shown in Table 1.

<Comparative Example 1>
The toner particles were prepared in the same manner as in Example 20, except that 0.1 parts by mass of a 38% aqueous solution of ferric chloride and a 0.1% aqueous cationic flocculant solution (manufactured by Daimei Chemical Co., Ltd., TC5002) were used. Then, toner particles 22, toner 22, and developer 22 were prepared and evaluated. The results are shown in Table 1.

<Comparative example 2>
When preparing toner particles, 1N sodium hydroxide was added until the pH reached 9.5, followed by 20 mass of Clewat TH (TTHA, triethylenetetramine hexaacetic acid, 10% diluted solution manufactured by Nagase Chemtech) as an ion sequestering agent. A toner particle 23, a toner 23, and a developer 23 were prepared and evaluated in the same manner as in Example 1 except that part of the sample was added. The results are shown in Table 1.

  As described above, in Examples 1 to 23, the occurrence of uneven gloss was suppressed even when an image was formed on a sheet having a large surface unevenness.

  DESCRIPTION OF SYMBOLS 1 Process cartridge, 3 Image forming apparatus, 10 Photoconductor, 12 Charging roll, 14 Cleaning roll, 16 Developing roll, 18 Transfer roll, 20 Cleaning blade, 24 High voltage power supply, 26 Transfer object, 28 Fixing apparatus, 30 Heating roll, 32 Pressure roll.

Claims (10)

Including resin and mold release agent,
When the storage elastic modulus at 100 ° C. is G ′ (100) and the storage elastic modulus at 200 ° C. is G ′ (200) in the toner frequency 6.28 Rad dynamic viscoelasticity measurement, G ′ (100) / G ′ ( 200) is in the range of 1 to 5, the electrostatic charge image developing toner.   In the differential thermal analysis of the toner, the endothermic peak temperature of the release agent is in the range of 50 ° C. or higher and 80 ° C. or lower, and the base is at a height of 10% of the peak height from the baseline in the endothermic peak of the release agent. 2. The electrostatic charge image developing toner according to claim 1, wherein a temperature range of a line drawn in parallel with the line is in a range of 10 ° C. or more and 20 ° C. or less.   The electrostatic charge image developing toner according to claim 1, wherein an acid value of the release agent is in a range of 3 mgKOH / g to 10 mgKOH / g.   4. The differential thermal analysis of the toner, wherein a difference between an endothermic peak temperature and an exothermic peak temperature of the release agent is in a range of 5 ° C. or more and 20 ° C. or less. The toner for developing an electrostatic charge image according to the item. A resin particle / release agent mixed dispersion preparation step of preparing a resin particle / release agent mixed dispersion in which resin particles containing a resin and a release agent are melt-mixed and dispersed;
An aggregating step of mixing the resin particle / release agent mixed dispersion and a colorant dispersion in which a colorant is dispersed to form aggregated particles;
A fusion step of fusing the aggregated particles by heating;
5. The method for producing a toner for developing an electrostatic charge image according to claim 1, comprising:   An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier.   A toner cartridge containing the electrostatic image developing toner according to claim 1. An image carrier, and developing means for developing the electrostatic latent image formed on the surface of the image carrier using a developer to form a toner image,
The process cartridge according to claim 6, wherein the developer is an electrostatic charge image developing developer according to claim 6. An image carrier, a latent image forming unit that forms an electrostatic latent image on the surface of the image carrier, a developing unit that develops the electrostatic latent image using a developer to form a toner image, and the development A transfer means for transferring the toner image thus transferred to the transfer body,
The image forming apparatus according to claim 6, wherein the developer is a developer for developing an electrostatic image according to claim 6. Residual toner removing means for removing residual toner remaining on the surface of the image carrier after transfer;
Collecting residual toner removed by the residual toner removing means and supplying the collected residual toner to the developing means;
The image forming apparatus according to claim 9, further comprising:

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