JP2009217053A - Electrostatic developing toner, electrostatic developing developer, toner cartridge, process cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic developing toner that ensures improved high temperature fixability and improved cleanability while satisfying low temperature fixing. <P>SOLUTION: The electrostatic developing toner contains two or more types of binding resins, a colorant and a lubricant, and satisfies the following formula (1): 150≤(MwS/MwT)×100≤200, where MwT is the weight average molecular weight of the toner, MwS is the weight average molecular weight of a toner classified to have a volume average particle size in the range of (1/5)×D50T to (2/3)×D50T, and D50T is the volume average particle size of the entire toner. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic charge developing toner (hereinafter also referred to as electrophotographic toner), a metallic gloss toner, an electrostatic charge developing developer, a toner cartridge, a process cartridge, and an image forming apparatus.

  In electrophotography, an electrostatic charge is formed on a photoreceptor by charging and exposure processes, the electrostatic charge is developed with a developer containing toner to form a toner image, and the toner image is transferred and fixed on a recording medium. Form an image. The developer used here includes a two-component developer comprising a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone. In the production of toner, a so-called kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded together with a release agent such as a pigment, a charge control agent, and a wax, cooled, finely pulverized, and further classified. Yes.

  In the toner prepared by the usual kneading and pulverizing method, the shape of the toner particles is indeterminate, and the surface structure of the toner particles slightly changes depending on the pulverization properties of the materials used and the conditions of the pulverization process. It is difficult to intentionally control the shape and surface structure.

  On the other hand, in recent years, a toner manufacturing method using a wet manufacturing method has been proposed as a means capable of intentionally controlling the shape and surface structure of the toner. Examples of the wet production method include a wet spheronization method capable of controlling the shape, a suspension granulation method capable of controlling the surface composition, a suspension polymerization method capable of controlling the internal composition, and an agglomeration and coalescence method.

  On the other hand, in recent years, toners that are particularly excellent in fixability (for example, low-temperature fixability) and offset resistance have been desired, and toners that combine a high molecular weight component and a low molecular weight component have been proposed as described below. For example, Patent Document 1 includes (A) 50 to 94.8% by weight of a styrene polymer containing 60% by weight or more of a styrene monomer and having a weight average molecular weight of 40,000 or less, and (B) a styrene monomer. A styrene polymer having a weight average molecular weight of 100,000 or more and 0.2 to 10% by weight of (C) (meth) acrylic acid ester monomer, Crosslinking (meth) acrylic acid ester polymer or (D) (meth) acrylic acid ester monomer having a weight average molecular weight of 100,000 or more and 60% by weight or more and a gel fraction of 20% by weight or more ( A toner composed of 5 to 49.8% by weight of a (meth) acrylate polymer has been proposed.

In Patent Document 2, in a developer for electrostatic charge development having toner particles containing at least a binder resin and magnetic iron oxide, and an inorganic fine powder, the binder resin comprises a high molecular weight component and a low molecular weight component. (A) The glass transition point of the high molecular weight component is 5 to 15 ° C. higher than the glass transition point of the low molecular weight component, and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the high molecular weight component Is 700,000 to 1.3 million, the peak molecular weight (PMw) is 400,000 to 1.1 million, the weight average molecular weight (Mw) / number average molecular weight (Mn) is 4.5 or less, and the Z average molecular weight ( Mz) is 1 million to 10 million, MI is substantially 0, (b) the low molecular weight component has Mw of 5500 to 30000, PMw of 5000 to 25000, Mw / Mn value 4.0 or less, the inorganic fine powder, the silica particles A, which is treated with at least silicone oil, and a silica particle B which has been treated with at least silicone oil, the average particle diameter D of the silica particles B _B is an average particle diameter larger electrostatic latent image developing developer 10 times more than D _a of the silica particles a have been proposed.

  Patent Document 3 discloses a toner containing a low molecular weight resin, a high molecular weight resin, and a colorant, in which resin fine particles made of a high molecular weight resin are unevenly distributed near the surface of the toner particles, and the peak molecular weight of the low molecular weight resin is A toner having a molecular weight of 1,000 to 30,000 and a peak molecular weight of a high molecular weight resin of 50,000 to 1,000,000 has been proposed.

  Patent Document 4 proposes a toner exhibiting a gold color, which is a toner including at least a binder resin and a colorant, and the colorant has an average thickness of 2 to 5 μm and an average length in the longitudinal direction of 15 to 500 μm. A gold toner for electrostatic charge development, which is a glitter pigment in which silver is coated on a flat glass flake, is disclosed.

Japanese Patent Laid-Open No. 8-128302 Japanese Patent Laid-Open No. 9-80796 JP 2000-292978 A JP 2003-207941 A

  The main purpose of the present invention is to improve the fixing property at high temperature and improve the cleaning properties by improving the strength of the toner fine powder, and in particular, uniform gloss when a metal foil or the like is added. It is an object of the present invention to provide an electrostatic charge developing toner, a developer for electrostatic charge development, a toner cartridge, a process cartridge, and an image forming apparatus that are strict.

  The present invention is as follows.

(1) Contains two or more types of binder resin, colorant, and release agent, the volume average particle diameter of the whole toner is D50T, the weight average molecular weight of the toner is MwT, and the toner is classified to obtain a volume average particle diameter. (1/5) × D50T or more and (2/3) × D50T or less in weight average molecular weight MwS, MwT and MwS satisfy the relationship of the following formula (1) Toner.
150 ≦ (MwS / MwT) × 100 ≦ 200 (1)

  (2) The electrostatic charge developing toner according to (1), wherein the binder resin is a polyester resin.

  (3) The electrostatic charge developing toner according to (1), wherein the small particle size side number particle size distribution index GSDp-under is in the range of 1.15 to 1.30.

  (4) In the electrostatic charge developing toner according to the above (1) to (3), the colorant is a metal foil having a thickness of 1 nm to 10 nm and a longitudinal direction of 80 nm to 1500 nm. Is a toner for developing an electrostatic charge.

  (5) In the electrostatic charge developing toner according to the above (4), the surface of the metal foil is coated with a resin compatible with a release agent, and the crystallinity of the release agent is 80 or more. This is an electrostatic charge developing toner.

  (6) The electrostatic charge developing toner according to (4) or (5), wherein the metal foil is any one of gold, silver, and copper.

  (7) The electrostatic charge developing toner according to any one of (1) to (6) above and a carrier having a volume average particle size distribution index GSDv in the range of 1.15 to 1.35. It is a developer for electrostatic charge development.

  (8) A toner cartridge that contains at least toner, and the toner is the electrostatic charge developing toner according to any one of (1) to (6).

  (9) A process cartridge including at least a developer holder and containing the developer for electrostatic charge development according to (7).

  (10) A latent image holding member, developing means for developing the electrostatic charge formed on the latent image holding member as a toner image with a developer, and the toner image formed on the latent image holding member on the transfer member Transfer means for transferring the toner image, fixing means for fixing the toner image transferred onto the transfer target, and cleaning means for cleaning the transfer residual component by rubbing the latent image holding member with a cleaning member, In the image forming apparatus, the developer is the developer for electrostatic charge development described in (7).

  According to the present invention, by making the weight average molecular weight (MwS) of the toner on the fine powder side larger than the weight average molecular weight MwT of the whole toner, for example, the influence of toner crushing when sandwiched between cleaning blades is reduced, and the cleaning characteristics are reduced. To improve. In addition, the toner on the fine powder side is easily melted by heating at the time of high-temperature fixing. However, since the fine powder toner is composed of a high molecular weight resin, it is composed of lower molecules than the fine powder toner. It is hard to melt compared with the toner on the coarse powder side. Therefore, a difference in the meltability between the fine powder side toner and the coarse powder side toner is unlikely to occur, so that the fixing characteristics of the entire toner, particularly in the high temperature region, are improved.

  In particular, according to the electrostatic charge developing toner of claim 4, the metal foil as the colorant is not exposed from the toner surface, thereby preventing charge leakage and maintaining the chargeability of the toner. Can do. According to the electrostatic charge developing toner of claim 5, the surface of the metal foil is coated with a resin compatible with the release agent, and the crystallinity of the release agent is increased, thereby fixing the toner during fixing. The metal foil is developed on the surface of the fixed image on the force of the low-viscosity liquid release agent flowing on the surface of the fixed image, and thereby the metal foil is oriented in the fixing toner to exhibit a metallic luster.

<Toner for electrostatic charge development>
The electrostatic charge developing toner of the present embodiment (hereinafter sometimes abbreviated as “toner”) contains two or more binder resins, a colorant, and a release agent, and has a volume average particle diameter of the whole toner. D50T, the weight average molecular weight of the toner is MwT, and the toner is classified so that the volume average particle diameter is in the range of (1/5) × D50T or more (2/3) × D50T or less. The weight average molecular weight of the toner is MwS. MwT and MwS satisfy the relationship of the following formula (1).
[Equation 1]
150 ≦ (MwS / MwT) × 100 ≦ 200 (1)

  When (MwS / MwT) × 100 is smaller than 150, the molecular weight of the fine powder side toner shifts to the low molecular weight side, and the strength of the fine powder side toner becomes low, so that the toner is easily crushed, and as a result, the cleaning characteristics are deteriorated. . Further, since the molecular weights of the toner on the fine powder side and the toner on the coarse powder side are approximate, the toner on the fine powder side melts faster during high-temperature fixing, which may reduce the fixability of the entire toner. . On the other hand, if (MwS / MwT) × 100 exceeds 200, the weight average molecular weight MwS of the toner on the fine powder side becomes too larger than the weight average molecular weight MwT of the whole toner. The toner may be melted later than the toner on the side, and the fixability of the entire toner may be lowered. As a result, there is a possibility that a mottled pattern resulting from insufficient melting of the fine powder side toner, particularly an image non-uniformity when a metal foil is used.

  The above-mentioned “range of volume average particle diameter of (1/5) × D50T or more (2/3) × D50T or less” is an effective range for confirming the ratio of the binder resin on the fine powder side by the classification means. Stipulated as

  In the electrostatic charge developing toner of this embodiment, the binder resin is a polyester resin. In addition, as for the said polyester resin, only the amorphous polyester mentioned later may be used, or the combination of the crystalline polyester resin mentioned later and an amorphous polyester resin may be used.

  Further, in the electrostatic charge developing toner of the present embodiment, the small particle size side number particle size distribution index GSDp-under is in the range of 1.15 to 1.30. Here, the “small particle size side number particle size distribution index GSDp-under” is obtained by measuring the particle size of 50% from the small particle size side of the number particle size distribution measured by the toner particle size distribution measurement method described later by the same measurement method. It is a value obtained by dividing the number particle size distribution by the particle size of 16% from the smaller diameter side.

  It is difficult to produce a toner having a small particle size side number particle size distribution index GSDp-under of less than 1.15. On the other hand, if the small particle size side number particle size distribution index GSDp-under exceeds 1.30, the toner Since the amount of fine powder increases with respect to the whole, the cleaning property is deteriorated, the high temperature fixing property is deteriorated, and toner fog may occur in the transferred image, and there is a possibility that the inside of the copying machine or the like is contaminated.

As the range of the coagulation value of the binder resin, the coagulation value of the high molecular weight resin fine particle dispersion is larger than that of the low molecular weight resin dispersion, and the coagulation value is in the range of 1 × 10 ⁻⁵ or more and 1 × 10 ⁻¹ or less. Is preferred. Here, the concentration at which the dispersion becomes unstable at a certain concentration and causes agglomeration is called a coagulation value.

  The coagulation value is the minimum amount of magnesium chloride (mol / g resin) required to agglomerate 1 g of resin particles in an emulsion having a solid concentration of 10% by mass, pH 7, and 25 ° C. Shows that the particles (resin particles) are stable in dispersion (hard to agglomerate)

In order to agglomerate the resin particles, the coagulation value needs to be within a certain range. If the coagulation value is smaller than 1 × 10 ⁻⁵ , it becomes difficult to maintain the particles due to destabilization of the resin particles. The diameter becomes extremely difficult to control. On the other hand, if it is larger than 1 × 10 ⁻¹ , the resin particles are very stabilized, and aggregation between the particles is difficult to occur, and the control of the particle size becomes difficult.

  When a polyester resin is used as the binder resin, the coagulation value is changed by changing the amount of sodium hydroxide used for transfer emulsification. Further, since the binder resin is a polyester resin, the coagulation value of the resin fine particles can be controlled. Further, in combination with the aggregation / unification method, the aggregation property of the resin fine particles can be controlled, and the toner can be produced so as to be composed of a polymer resin on the toner fine powder side.

  In addition, another electrostatic charge developing toner according to the present embodiment is a metal foil having a film thickness of 1 nm or more and 10 nm or less and a longitudinal direction of 80 nm or more and 1500 nm or less. It is a metallic gloss toner, and if necessary, the surface of the metal foil is coated with a resin compatible with the mold release agent, and the crystallinity of the mold release agent is 80 or more.

  The metal foil may be any foil, but is preferably any one of gold, silver, and copper, for example.

  When the metal foil is larger than the above-mentioned film thickness and size in the longitudinal direction, considering the normal toner particle size, a part of the metal foil is exposed from the toner surface and the charge is leaked. Becomes unstable. On the other hand, there is no metal foil smaller than the above thickness at present, and a metal foil having a longitudinal size smaller than the above range does not exhibit metallic luster even when oriented.

  In addition, when the crystallinity of the release agent is less than 80, since the low viscosity liquid release agent is weakly swept to the fixed image surface during fixing, the metal foil is not easily developed on the fixed image surface. As a result, the metal foil is not oriented in the fixing toner, and the desired metallic luster is not exhibited.

  Further, by coating the surface of the metal foil with a resin compatible with the release agent, the metal foil is prevented from being left inside the toner accompanying the flow of the release agent. The resin used for coating is preferably the same type as the mold release agent, more preferably the same type and a resin having a crystallinity of 20 or more. For example, when there is no difference in viscosity between the resin and the release agent at the time of melting, it is difficult to develop the metal foil in a certain direction. Therefore, it is more desirable to use a resin having a high viscosity.

  Hereinafter, components constituting the toner of the exemplary embodiment will be described in detail.

  As described above, the components constituting the toner of the present embodiment include amorphous polyesters, colorants, and release agents, but other components may be included as necessary.

<Binder resin>
In the electrostatic charge developing toner of the present embodiment, from the viewpoint of low-temperature fixability, an amorphous polyester may be used as a binder resin. On the other hand, a crystalline resin, a crystalline polyester resin, and an amorphous polyester described later are used. A combination with a resin may be used.

[Amorphous polyester]
As the amorphous polyester used in the toner of the present embodiment, a known amorphous polyester can be used.

  The range of the glass transition temperature (Tg) of the amorphous polyester is preferably 50 ° C. or higher and 80 ° C. or lower, more preferably 55 ° C. or higher and 65 ° C. or lower. If the glass transition temperature (Tg) is lower than 50 ° C., it may be difficult to store the toner. If the glass transition temperature (Tg) is higher than 80 ° C., the effect of low-temperature fixability may not be obtained.

  The weight average molecular weight (Mw) of the amorphous polyester is preferably in the range of 8000 to 30000, but the weight average molecular weight (Mw) is in the range of 8000 to 16000 from the viewpoint of low temperature fixability and mechanical strength. It is more preferable that The third component may be copolymerized from the viewpoints of low-temperature fixability and mixing properties.

  The method for producing an amorphous polyester is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component, and is not particularly limited by the production method described later, and can be produced by a general polyester polymerization method. .

  As the acid (dicarboxylic acid) component used for the synthesis of the amorphous polyester, various dicarboxylic acids described later can be similarly used.

  The acid (dicarboxylic acid) component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear dicarboxylic 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, 1,10-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 An acid anhydride is mentioned, However, It is not limited to these.

  The acid (dicarboxylic acid) component may include components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component 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. Is also included. The dicarboxylic acid component having a sulfonic acid group includes a component derived from a dicarboxylic acid having a sulfonic acid group, a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, or an acid anhydride. Is also included.

  The dicarboxylic acid having a double bond can be suitably used 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 dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce fine particles, it can be emulsified or suspended without using a surfactant, as will be described later. Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt and the like are preferable in terms of cost.

  As the alcohol (diol) component, various diols used for the synthesis of an amorphous polyester resin can be used.

  The alcohol (diol) component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto.

  On the other hand, examples of other components included as necessary include diol components having a double bond and diol components 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.

  When adding an alcohol (diol) component other than these linear aliphatic diol components, the content of (diol component having a double bond and / or diol component having a sulfonic acid group) in the alcohol (diol) component The amount is preferably from 1 to 20 mol%, more preferably from 2 to 10 mol%. 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, when it exceeds 20 mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the storage stability of the toner is deteriorated, or the emulsion particle size is too small to be dissolved in water, and no latex is produced. There is a case.

  In addition to the above aliphatic diols, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, etc. Although it can be used, it is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct from the viewpoint of toner productivity, heat resistance, and transparency. Moreover, both an acid (dicarboxylic acid) component and an alcohol component may contain a plurality of components. In particular, bisphenol S has an effect of improving heat resistance.

  The method for producing the amorphous polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. They are manufactured using different types of monomers. 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 amorphous polyester can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation. 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 is distilled off. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Catalysts that can be used in the production of the amorphous polyester 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, and specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  In addition to the polymerizable monomer described above, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like may be used for the purpose of adjusting the melting point, molecular weight, etc. of the amorphous polyester.

  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′-dibenzoic 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 and diglycolic acid. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

  In addition, a monofunctional monomer may be introduced into the crystalline polyester for the purpose of blocking the polar group at the terminal of the amorphous polyester and improving the environmental stability of the toner charging characteristics.

  Monofunctional monomers include benzoic acid, chlorobenzoic acid, bromobenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tertiary butyl. Benzoic acid, naphthoic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid, stearyl acid, and lower Monocarboxylic acids such as alkyl esters; or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols can be used.

<Colorant>
Known colorants can be used as the colorant used in the toner of the exemplary embodiment. For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, hansa yellow, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Can be given.

  Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

  Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C Rose Bengal, Eoxin Red, Alizarin Lake and the like.

Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, indanthrene blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. For example, a rater.
Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.

  Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.

Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine. Furthermore, these can be used alone or in combination and further in a solid solution state.

  Further, in order to obtain a toner having a metallic luster, the above-described metal foil is used as a colorant.

  These colorants are dispersed by a known method, and for example, a rotary shear type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.

  Further, these colorants are dispersed in an aqueous system by the homogenizer using a polar surfactant.

  The colorant of the present embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, and dispersibility in the toner. The added amount of the colorant is 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  When a magnetic material is used for the black colorant, 30 to 100 parts by mass is added unlike other colorants.

  Further, when the toner is used as magnetism, magnetic powder may be contained. As such magnetic powder, a substance magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite.

  In particular, in this embodiment, in order to obtain toner in the aqueous layer, it is necessary to pay attention to the water layer's ability to migrate, dissolve, and oxidize, and surface modification, such as hydrophobization treatment, is preferably performed. It is preferable to keep it.

[Release agent]
When a release agent is present in the toner, the releasability at the time of fixing is improved, and variations in the releasability due to pressure at the time of fixing can be reduced. The release agent that can be used in the embodiment of the present invention is not particularly limited, but low molecular weight polyolefin wax such as polyethylene, polypropylene, polybutene, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Plant minerals such as beeswax, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc., petroleum wax, and modified products thereof Can do. Paraffin wax, microcrystalline wax, and polyolefin wax are preferable, and paraffin wax and polyethylene wax are particularly preferable.

  The release agent has a crystallinity of 80 or more. The crystallinity of the release agent was measured by, for example, a minute high temperature X-ray diffractometer “RINT-1500V” (manufactured by Rigaku Corporation).

  The mold release agent preferably has a freezing point measured according to ASTM D938 of 50 ° C. or higher and 100 ° C. or lower. More preferably, it is 60 degreeC or more and 90 degrees C or less.

  The melt viscosity of the release agent used in the embodiment of the present invention is 1 mPa · s or more and 10 mPa · s or less at 120 ° C. A more preferable range of the melt viscosity of the release agent is 2 mPa · s or more and 8 mPa · s or less under the same conditions. When it is within this range, the release property when combined with the fiber is good, which is preferable. The viscosity of the release agent at 120 ° C. is measured with an E-type viscometer. For the measurement, an E-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) equipped with an oil circulation thermostat and a cone plate is used. The cone plate uses a cone angle of 1.34 °. A sample is put into the cup, the temperature of the circulation device is set to 120 ° C., an empty measurement cup and cone are set to the measurement device, and the temperature is kept constant while circulating the oil. When the temperature is stabilized, 1 g of the sample is put in the measuring cup, and the cone is allowed to stand still for 10 minutes. After stabilization, rotate the cone and measure. The rotational speed of the cone is 60 rpm. The measurement is performed three times, and the average value is taken as the viscosity. Moreover, these mold release agents may be used individually by 1 type, and may be used together 2 or more types.

  The content of the release agent is preferably in the range of 3 to 20 parts by mass, and more preferably in the range of 5 to 18 parts by mass with respect to 100 parts by mass of the binder resin. If the content of the release agent is less than 3 parts by mass, the effect of adding the release agent is not obtained, and hot offset at a high temperature may be caused. On the other hand, when the amount exceeds 20 parts by mass, the charging property is adversely affected, and the mechanical strength of the toner is reduced. Therefore, the toner is easily destroyed by stress in the developing machine, and may cause carrier contamination.

<Other ingredients-various additives>
Other components used in the toner in the exemplary embodiment are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include various known additives such as a charge control agent. Known external additives such as inorganic fine particles and organic fine particles can be added to the toner in the present exemplary embodiment as necessary.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples include Bengala, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among them, silica fine particles and titanium oxide fine particles are preferable, and hydrophobized fine particles are particularly preferable.

  Inorganic fine particles are generally used for the purpose of improving fluidity. The primary particle diameter of the inorganic fine particles is preferably in the range of 1 nm to 200 nm, and the addition amount thereof is in the range of 0.01 parts by weight to 20 parts by weight with respect to 100 parts by weight of the toner. It is preferable.

  Organic fine particles are generally used for the purpose of improving cleaning properties and transfer properties, and specific examples include polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and the like.

<Toner production method>
The toner of the present embodiment can be produced by an aggregation / unification method.

  Examples of the toner manufacturing method in the present embodiment include, for example, amorphous polyester resin fine particles, resin fine particle dispersion in which crystalline polyester resin fine particles are dispersed and mixed, colorant fine particle dispersion in which colorant fine particles are dispersed, and release It has an agglomeration step of mixing the release agent fine particle dispersion in which the fine agent particles are dispersed to form aggregated particles of the resin fine particles, the colorant fine particles and the release agent fine particles, and further adjusting the pH in the aggregation system to agglomerate The production method includes a stopping step for stopping the growth, and a step of heating and aggregating and aggregating the aggregated particles to a temperature equal to or higher than the glass transition temperature of the resin fine particles, and further using at least water as the base toner obtained. You may have the process of wash | cleaning and the process of drying the wash | cleaned base toner. In addition, the aggregation / unification method may have a shell forming step of adding other resin fine particles to adhere to the surface of the aggregated particles after the aggregation step, if necessary.

  Hereinafter, each process in an example of the aggregation / unification method mentioned above is demonstrated in detail. The toner manufacturing method in the present embodiment is not limited to this.

[Aggregation process]
In the aggregation step, first, a resin fine particle dispersion, a colorant fine particle dispersion, and a release agent fine particle dispersion are prepared.

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

  Further, the resin particle dispersion is obtained by dissolving an amorphous polyester resin in a mixed solution of a good solvent and a water-soluble poor solvent, neutralizing it with ammonia, and then adding water dropwise to perform phase inversion emulsification. It is preferable to use a polyester resin emulsion dispersion.

<Transfer emulsification method>
The transfer emulsification method described above will be described below. In the phase inversion emulsification method, at least the above-described amorphous polyester resin is dissolved in a mixed solution of an organic solvent (good solvent) and a water-soluble solvent (water-soluble poor solvent), and a neutralizer (in this embodiment) is used as necessary. In the form, ammonia) or a dispersion stabilizer is added, and under stirring, a water-soluble solvent (for example, water) is added dropwise to obtain emulsified particles, and then the solvent in the resin dispersion is removed to obtain an emulsion. Is the way to get. At this time, the order of adding the neutralizing agent and the dispersion stabilizer may be changed.

  Examples of the organic solvent (resin dissolving solvent) for dissolving the amorphous polyester resin include formic acid esters, acetic acid esters, butyric acid esters, ketones, ethers, benzenes, and halogenated carbons. Specifically, esters such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl such as formic acid, acetic acid, butyric acid, acetone, MEK, MPK, MIPK, MBK, MIBK Such as methyl ketones, ethers such as diethyl ether and diisopropyl ether, heterocyclic substituents such as toluene, xylene and benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene , Chloroform, monochlorobenzene, dichloroethylidene, and other halogenated carbons can be used singly or in combination of two or more. To low-boiling solvents such as acetates, methyl ketones and ethers. Used preferred, in particular, acetone, methyl ethyl ketone, acetic acid, ethyl acetate, butyl acetate is preferred. When the organic solvent remains in the resin fine particles, it becomes a VOC causative substance even in a small amount, and it is preferable to use a solvent having a relatively high volatility.

  As the water-soluble solvent, ion-exchanged water is basically used, but a water-soluble organic solvent may be included so as not to destroy the oil droplets. Examples of water-soluble organic solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-pentanol and other short carbon chain alcohols; ethylene glycol monomethyl ether, ethylene glycol Examples include ethylene glycol monoalkyl ethers such as monoethyl ether and ethylene glycol monobutyl ether; ethers, diols, THF, acetone and the like. The mixing ratio of these water-soluble organic solvents to ion-exchanged water is preferably 1% or more and 50% or less, and preferably 1% or more and 30% or less, and is used as an aqueous component. In addition, the water-soluble organic solvent may be added to the resin solution and used in addition to the ion-exchanged water to be added. In the case of adding a water-soluble organic solvent, the wettability between the resin and the resin dissolving solvent can be adjusted, and a function of reducing the liquid viscosity after the resin is dissolved can be expected.

  If necessary, a dispersant may be added to the resin solution and the aqueous component so that the emulsion is stably dispersed. As the dispersant, a hydrophilic colloid is formed in an aqueous component, and in particular, cellulose derivatives such as hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose; polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylate, Examples thereof include synthetic polymers such as polymethacrylate, and dispersion stabilizers such as gelatin, gum arabic, and agar. Solid fine powders such as silica, titanium oxide, alumina, tricalcium phosphate, calcium carbonate, calcium sulfate, and barium carbonate can also be used. These dispersion stabilizers are usually added so that the concentration in the aqueous component is 0 to 20% by mass, preferably 0 to 10% by mass.

  A surfactant is also used as the dispersant. As examples of the surfactant, those similar to those used in the colorant dispersion described later can be used. For example, in addition to natural surfactant components such as saponin, cationic surfactants such as alkylamine hydrochlorides / acetates, quaternary ammonium salts, glycerols, fatty acid soaps, sulfates, alkylnaphthalene sulfonates, sulfones Anionic surfactants such as acid salts, phosphoric acid, phosphate esters, sulfosuccinates and the like can be mentioned, and anionic surfactants and nonionic surfactants are preferably used. In order to adjust the pH of the emulsion, a neutralizing agent may be added. As the neutralizing agent, general acids such as nitric acid, hydrochloric acid, sodium hydroxide and ammonia, and alkalis can be used.

  As a method for removing the organic solvent from the emulsion, a method in which the organic solvent is volatilized at room temperature or under heating, and a method in which this is combined with reduced pressure are preferably used.

  The colorant fine particle dispersion is prepared by dispersing colorant fine particles of a desired color such as blue, red, and yellow in a solvent using an ionic surfactant.

  In addition, the release agent fine particle dispersion is obtained by dispersing the release agent together with a polymer electrolyte (for example, an ionic surfactant, a polymer acid, or a polymer base) in water and heating it above the melting point of the release agent. At the same time, the fine particles are adjusted by a homogenizer or a pressure discharge type disperser that can be subjected to strong shearing.

  Next, the resin fine particle dispersion, the colorant fine particle dispersion, and the release agent fine particle dispersion are mixed, and the resin fine particles, the color fine agent particles, and the release agent fine particles are hetero-agglomerated to obtain a diameter that is approximately close to the desired toner diameter. Aggregated particles having a core (core aggregated particles) are formed. Here, the pH is preferably 4.5 or more and 6.0 or less so that the difference in the coagulation value of the resin fine particles becomes remarkable. When the pH is less than 4.5, the cohesiveness of the resin fine particles becomes uniform and is not unevenly distributed, so that a toner satisfying the above-described formula (1) cannot be obtained. On the other hand, when the pH exceeds 6.0, the cohesiveness of the resin fine particles is deteriorated, the toner GSDp-under is increased, and a lot of toner fine powder is present. As a result, the transfer image is fogged and the cleaning property is also improved. Deteriorate.

  Here, the volume average particle diameter of the resin fine particles, the colorant fine particles, and the release agent fine particles used in the aggregation step is 1 μm or less in order to easily adjust the toner diameter and the particle size distribution to desired values. It is preferable that it is within a range of 100 to 300 nm.

  The volume average particle size is measured using a laser diffraction type laser diffraction type particle size distribution measuring device (LA-700: manufactured by Horiba, Ltd.). As a measurement method, a sample in a dispersion is adjusted 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 particles is stopped by adjusting the pH in the aggregation system. Specifically, the growth of the particles is stopped by adjusting the pH in the aggregation system to 6-9.

[Fusion / unification process]
In the fusion and coalescence process, first, the glass transition temperature of the resin fine particles contained in the aggregated particles in the solution containing the aggregated particles obtained through the aggregation process and the shell formation process performed as necessary. The base toner is obtained by heating to the above temperature and fusing and uniting.

[Washing process]
In the washing step, the base toner particle dispersion obtained in the fusion / unification step is at least subjected to substitution washing with ion-exchanged water to perform solid-liquid separation. Although there is no restriction | limiting in particular in a solid-liquid separation method, From the point of productivity, suction filtration, pressure filtration, etc. are used preferably.

[Drying process]
In the drying process, the solid-liquid separated wet cake is dried to obtain base toner particles. Although there is no restriction | limiting in particular in a drying method, From the point of productivity, freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying, etc. are used preferably.

  In addition, when producing a metallic glossy toner for electrostatic charge development, a colorant fine particle dispersion in which a metal foil as a colorant is dispersed and a release agent fine particle dispersion are used, and the colored release particles which are these aggregated particles are previously used. Molding agent particles are produced, and then the colored release agent particle dispersion and the resin fine particle dispersion are agglomerated according to the agglomeration process described above to produce toner particles.

<Developer for electrostatic charge development>
The developer for developing electrostatic charge of the present embodiment is not particularly limited except that it contains the toner for developing electrostatic charge of the present embodiment described above, and can have an appropriate component composition according to the purpose. The electrostatic charge developing developer of the present invention becomes a one-component electrostatic charge developing developer when the electrostatic charge developing toner is used alone, and when used in combination with a carrier, it is a two-component electrostatic charge developing developer. Becomes a developer.
Hereinafter, the developer for electrostatic charge development according to the present embodiment (hereinafter may be abbreviated as “developer”) will be described.

  There is no restriction | limiting in particular as a carrier, A well-known carrier can be used. Examples of the carrier include a resin-coated carrier having a resin coating layer in which a core resin surface is coated with a coating resin. The carrier may be a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin.

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

  Examples of the conductive material include metals (for example, gold, silver, copper, etc.), carbon black, titanium oxide, zinc oxide, barium sulfide, aluminum borate, potassium titanate, tin oxide, carbon black, and the like. However, it is not limited to these.

  In addition, examples of the carrier core material include magnetic metals (for example, iron, nickel, cobalt, etc.), magnetic oxides (for example, ferrite, magnetite, etc.), glass beads, etc., because the carrier is used for the magnetic brush method. In this case, the core material of the carrier is preferably a magnetic material. The volume average particle size of the core material of the carrier is preferably in the range of 10 μm to 500 μm, and more preferably in the range of 30 μm to 100 μm.

  In order to coat the surface of the carrier core with a resin, a method of coating with a coating layer forming solution in which a coating resin and, if necessary, various additives are dissolved in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be appropriately selected in consideration of the coating resin to be used, application suitability, and the like.

  Specific resin coating methods include (1) a dipping method in which a carrier core material is immersed in a coating layer forming solution, (2) a spray method in which the coating layer forming solution is sprayed on the surface of the carrier core material, 3) Fluidized bed method in which the coating layer forming solution is sprayed in a state where the carrier core material is floated by flowing air. (4) The carrier core material and the coating layer forming solution are mixed in a kneader coater, and the solvent is added. The kneader coater method to remove is mentioned.

  The volume average particle size distribution index GSDv of the carrier is in the range of 1.15 to 1.35. The GSDv is measured by a measurement method similar to the toner particle size distribution measurement method described later.

  The mixing ratio (weight ratio) of the toner and the carrier in the developer containing the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100. preferable.

<Image forming apparatus>
Next, an example of the image forming apparatus according to the present embodiment will be described.

  FIG. 1 is a schematic diagram illustrating a configuration example of an image forming apparatus for forming an image by the image forming method of the present embodiment. In the illustrated image forming apparatus 200, four electrophotographic photosensitive members 401 a to 401 d are disposed in parallel in the housing 400 along the intermediate transfer belt 409. The electrophotographic photoreceptors 401a to 401d form, for example, images in which the electrophotographic photoreceptor 401a is yellow, the electrophotographic photoreceptor 401b is magenta, the electrophotographic photoreceptor 401c is cyan, and the electrophotographic photoreceptor 401d is black. Is possible.

  Each of the electrophotographic photosensitive members 401a to 401d can be rotated in a predetermined direction (counterclockwise on the paper surface), and the charging rolls 402a to 402d, the developing devices 404a to 404d, and the primary transfer roll 410a along the rotation direction. To 410d and cleaning blades 415a to 415d are arranged. Each of the developing devices 404a to 404d can be supplied with toner of four colors of black, yellow, magenta and cyan accommodated in the toner cartridges 405a to 405d, and the primary transfer rolls 410a to 410d are respectively intermediate transfer belts. 409 is in contact with the electrophotographic photoreceptors 401a to 401d.

  Further, an exposure device 403 is disposed at a predetermined position in the housing 400, and it becomes possible to irradiate the surfaces of the charged electrophotographic photoreceptors 401a to 401d with a light beam emitted from the exposure device 403. ing. Accordingly, charging, exposure, development, primary transfer, and cleaning are sequentially performed in the rotation process of the electrophotographic photosensitive members 401a to 401d, and the toner images of the respective colors are transferred onto the intermediate transfer belt 409 in an overlapping manner.

  Here, the charging rolls 402a to 402d contact the surface of the electrophotographic photoreceptors 401a to 401d with a conductive member (charging roll), and apply a voltage uniformly to the photoreceptor to charge the photoreceptor surface to a predetermined potential. (Charging process). In addition to the charging roll shown in this embodiment, charging by a contact charging method may be performed using a charging brush, a charging film, a charging tube, or the like. Moreover, you may charge by the non-contact system using a corotron or a scorotron.

  As the exposure apparatus 403, an optical system apparatus or the like that can expose a light source such as a semiconductor laser, an LED (light emitting diode), a liquid crystal shutter, or the like on the surfaces of the electrophotographic photosensitive members 401a to 401d can be used. Among these, when an exposure apparatus capable of exposing non-interference light is used, interference fringes between the electroconductive substrates of the electrophotographic photoreceptors 401a to 401d and the photosensitive layer can be prevented.

  The developing devices 404a to 404d can be carried out using a general developing device that develops the developer for two-component electrostatic charge development in contact or non-contact with the developer (development process). Such a developing device is not particularly limited as long as a two-component electrostatic charge developing developer is used, and a known one can be appropriately selected according to the purpose. In the primary transfer process, a primary transfer bias having a polarity opposite to that of the toner carried on the image carrier is applied to the primary transfer rolls 410a to 410d, so that each color toner is transferred from the image carrier to the intermediate transfer belt 409. The primary transfer is performed sequentially.

  The cleaning blades 415a to 415d are for removing residual toner adhering to the surface of the electrophotographic photosensitive member after the transfer process, and the electrophotographic photosensitive member cleaned by this cleaning process is repeatedly used in the above-described image forming process. Is done. Examples of the material for the cleaning blade include urethane rubber, neoprene rubber, and silicone rubber.

  The intermediate transfer belt 409 is supported with a predetermined tension by a drive roll 406, a backup roll 408, and a tension roll 407, and can rotate without causing deflection due to the rotation of these rolls. Further, the secondary transfer roll 413 is disposed so as to contact the backup roll 408 via the intermediate transfer belt 409.

  By applying a secondary transfer bias having a reverse polarity to the toner on the intermediate transfer member to the secondary transfer roll 413, the toner is secondarily transferred from the intermediate transfer belt to the recording medium. The intermediate transfer belt 409 that has passed between the backup roll 408 and the secondary transfer roll 413 is cleaned by, for example, a cleaning blade 416 disposed near the drive roll 406 or a static eliminator (not shown). It is repeatedly used for the next image forming process. A tray (transfer medium tray) 411 is provided at a predetermined position in the housing 400, and the transfer medium 500 such as paper in the tray 411 is transferred to the intermediate transfer belt 409 and the secondary transfer roll by the transfer roll 412. Then, the paper is sequentially transferred between the two fixing rolls 414 that are in contact with each other and the two fixing rolls 414 that are in contact with each other.

  The image forming method of the present embodiment is formed on the surface of the latent image holding body using a latent image forming step for forming an electrostatic charge on the surface of the latent image holding body and a developer carried on the developer carrying body. A developing process for developing an electrostatic charge to form a toner image, a transfer process for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a toner image transferred to the surface of the transfer target And a fixing step of thermally fixing the toner, wherein the developer is at least a developer containing the electrostatic charge developing toner of the present invention. The developer may be either a one-component system or a two-component system.

  As each of the above steps, a known step in the image forming method can be used.

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

  In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

  The method for supplying the release agent to the surface of the roller or belt, which is a fixing member used for heat fixing, is not particularly limited. For example, a pad method using a pad impregnated with a liquid release agent, a web method, a roller method. Non-contact shower method (spray method) and the like, and the web method and the roller method are particularly preferable. These methods are advantageous in that the release agent can be supplied uniformly and it is easy to control the supply amount. In order to supply the release agent uniformly to the entire fixing member by the shower method, it is necessary to use a separate blade or the like.

  Examples of the transfer target (recording material) to which the toner image is transferred include plain paper and OHP sheet used for electrophotographic copying machines, printers, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited. In the examples, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.

(Toner particle size and particle size distribution measurement method)
In the present invention, the toner particle size and particle size distribution were measured using Multisizer II (Beckman-Coulter) as the measuring device and ISOTON-II (Beckman-Coulter) as the electrolyte.

  As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 to 150 ml of the electrolytic solution. The electrolyte solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of 2 to 60 μm particles is measured using the Multisizer II type with an aperture diameter of 100 μm. Thus, the volume average particle diameter, GSDv, and GSDp were obtained. The number of particles to be measured was 50,000.

(Volume average particle diameter of resin fine particles, colorant particles, etc.)
Volume average particle diameters of resin fine particles, colorant particles, and the like were measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

(Measurement method of weight average molecular weight and molecular weight distribution of resin)
In the present invention, the molecular weight and molecular weight distribution of the binder resin and the like are those obtained under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” 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 ”.

(Measurement method of glass transition temperature of resin)
The melting point of the crystalline polyester resin and the glass transition temperature (Tg) of the amorphous polyester resin were measured using a differential scanning calorimeter (manufactured by Perkin Elmer: DSC-7) according to ASTM D3418-8. It calculated | required from the maximum peak. The temperature correction of the detection part of this apparatus (DSC-7) uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. For the sample, an aluminum pan was used, an empty pan was set for control, the temperature was raised at a rate of temperature increase of 10 ° C./min, held at 150 ° C. for 5 minutes, and liquid nitrogen was used from 150 ° C. to 0 ° C. Onset temperature analyzed from the endothermic curve during the second temperature increase obtained by lowering the temperature at 10 ° C / min, holding at 0 ° C for 5 minutes, and increasing the temperature from 0 ° C to 150 ° C again at 10 ° C / min. Was Tg.

[Preparation of polymer polyester resin dispersion (1)]
Bisphenol A ethylene oxide 2 mol adduct: 38 parts by mass Bisphenol A propylene oxide 2 mol adduct: 27.5 parts by mass Dimethyl terephthalate: 25 parts by mass Dodecenyl succinic acid: 7 parts by mass Trimellitic acid: 2.5 parts by mass The above monomer was charged into a 5 liter flask equipped with a device, a nitrogen inlet tube, a temperature sensor, and a rectifying column. The temperature was raised to 190 ° C. over 1 hour, and the reaction system was uniformly stirred. Then, 1.0% by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised to 240 ° C. over 6 hours from the same temperature, and the dehydration condensation reaction was continued at 240 ° C. for another 2 hours, with a glass transition point of 58 ° C. and an acid value of 15. An amorphous polyester resin (1) having 0 mg KOH / g, a weight average molecular weight of 60,000, and a number average molecular weight of 5,800 was obtained.

Subsequently, the amorphous polyester resin (1) (Mw: 60,000) was used to prepare a polymer polyester resin dispersion (1). 160 parts by mass of amorphous polyester resin (1), 233 parts of ethyl acetate, and 0.1 part of aqueous sodium hydroxide solution (0.3N) were prepared, and these were put into a 500 ml separable flask. The mixture was heated at 70 ° C. and stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase inversion emulsification was carried out, and the solvent was removed to obtain a polymer polyester resin dispersion (1) (solid content concentration: 30%). . The coagulation value was 2.3 × 10 ⁻² . The volume average particle diameter of the resin particles in the polymer polyester resin dispersion (1) was 160 nm.

[Preparation of low molecular weight polyester resin dispersion (1)]
In a heat-dried two-necked flask, 71 parts of dimethyl adipate, 184 parts of dimethyl terephthalate, 206 parts of bisphenol A ethylene oxide adduct, 42 parts of biphenol, 27 parts of ethylene glycol and 0.036 parts of tetrabutoxy titanate as a catalyst Then, after introducing nitrogen gas into the container and keeping the temperature in an inert atmosphere, the temperature was raised and subjected to a copolycondensation reaction at 160 ° C. for about 10 hours, and then the temperature was raised to 220 ° C. while gradually reducing the pressure to 10 Torr and held for 8 hours. Thus, an amorphous polyester resin (2) was synthesized.

  It was 64 degreeC when the glass transition temperature of the obtained amorphous polyester (2) was measured using the differential scanning calorimetry system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester 2 was measured by GPC by the above-mentioned measuring method, the weight average molecular weight (Mw) was 15000 and the number average molecular weight was 4,400.

Amorphous polyester resin (2) (MW: 15,000) (160 parts), ethyl acetate (233 parts), and sodium hydroxide aqueous solution (0.3N) (0.1 part) were prepared. The mixture was placed in a bull flask, heated at 70 ° C., and stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inversion emulsification, and solvent removal were performed to obtain a low molecular weight polyester resin dispersion (1) (solid content concentration: 30%). . The coagulation value was 3.7 × 10 ⁻⁴ . The volume average particle diameter of the resin particles in the low molecular weight polyester resin dispersion (1) was 160 nm.

[Preparation of low molecular weight polyester resin dispersion (2)]
In a heat-dried two-necked flask, 74 parts of dimethyl adipate, 192 parts of dimethyl terephthalate, 216 parts of bisphenol A ethylene oxide adduct, 38 parts of ethylene glycol, and 0.037 parts of tetrabutoxy titanate as a catalyst are placed in a container. Nitrogen gas was introduced and the temperature was raised while stirring in an inert atmosphere, followed by a copolycondensation reaction at 160 ° C. for about 7 hours, and then the temperature was raised to 220 ° C. while gradually reducing the pressure to 10 Torr and held for 4 hours. . The pressure was returned to normal pressure, 9 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and held for 1 hour to synthesize amorphous polyester resin (3).

  It was 60 degreeC when the glass transition temperature of the obtained amorphous polyester (3) was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester (3) was measured using GPC by the above-described measurement method, the weight average molecular weight (Mw) was 12,000 and the number average molecular weight was 3,700.

Amorphous polyester resin (3) (MW: 12,000) (160 parts), ethyl acetate (233 parts), and sodium hydroxide aqueous solution (0.3N) (0.05 parts) were prepared. The mixture was placed in a bull flask, heated at 70 ° C., and stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inversion emulsification, and solvent removal were performed to obtain a low molecular weight polyester resin dispersion (2) (solid content concentration: 30%). . The coagulation value was 4.4 × 10 ⁻³ . Moreover, the volume average particle diameter of the resin particles in the low molecular weight polyester resin dispersion liquid (2) was 160 nm.

[Preparation of low molecular weight polyester resin dispersion (3)]
In a heat-dried two-necked flask, 72 parts of dimethyl adipate, 188 parts of dimethyl terephthalate, 211 parts of bisphenol A ethylene oxide adduct, 37 parts of ethylene glycol and 0.036 parts of tetrabutoxy titanate as a catalyst are placed in a container. Nitrogen gas was introduced and the temperature was increased while stirring in an inert atmosphere, followed by a co-condensation polymerization reaction at 160 ° C. for about 5 hours, and then the temperature was increased to 220 ° C. while gradually reducing the pressure to 10 Torr and maintained for 3 hours. . Once the pressure was returned to normal pressure, 18 parts of trimellitic anhydride was added, and the pressure was gradually reduced again to 10 Torr and maintained for 1 hour to synthesize an amorphous polyester resin (4).

  It was 56 degreeC when the glass transition temperature of the obtained amorphous polyester (4) was measured using the differential scanning calorific value system (DSC) with the above-mentioned measuring method. When the molecular weight of the obtained amorphous polyester (4) was measured using GPC by the above-described measurement method, the weight average molecular weight (Mw) was 8000, and the number average molecular weight was 2,300.

Amorphous polyester resin (4) (MW: 8,000) (160 parts), ethyl acetate (233 parts), and sodium hydroxide aqueous solution (0.3N) (0.4 parts) were prepared. The mixture was placed in a bull flask, heated at 70 ° C., and stirred with a three-one motor (manufactured by Shinto Kagaku Co., Ltd.) to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added, phase-inversion emulsification, and solvent removal were performed to obtain a low molecular weight polyester resin dispersion (3) (solid content concentration: 30%). . The coagulation value was 2.4 × 10 ⁻⁵ . Moreover, the volume average particle diameter of the resin particles in the low molecular weight polyester resin dispersion (3) was 155 nm.

[Preparation of colorant dispersion]
-Preparation of cyan colorant dispersion-
100 parts by mass of a cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)), 5 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and ion-exchanged water 300 The mixture was mixed with parts by mass and dispersed for 1 hour using a high-pressure impact disperser Ultimizer (HJP30006: manufactured by Sugino Machine Co., Ltd.) to obtain a cyan colorant dispersion.

  When the volume average particle diameter of the colorant (cyan pigment) in the obtained cyan colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, the volume average particle diameter was 171 nm. . The solid content ratio of the cyan colorant dispersion was 24.2% by weight.

-Preparation of yellow colorant dispersion-
100 parts by mass of yellow pigment (CI Pigment Yellow 74: manufactured by Dainichi Seika), 10 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R) and 300 parts by mass of ion-exchanged water are mixed. Then, using a high-pressure impact disperser Ultimizer (HJP30006: manufactured by Sugino Machine Co., Ltd.), the mixture was dispersed for 1 hour to obtain a yellow colorant dispersion.

  When the volume average particle size of the colorant (yellow pigment) in the obtained yellow colorant dispersion was measured using a laser diffraction particle size measuring instrument by the above-described measurement method, the volume average particle size was 189 nm. . Further, the solid content ratio of the yellow colorant dispersion was 24.3% by weight.

-Preparation of magenta colorant dispersion-
100 parts by mass of a magenta pigment (CI Pigment Red 122: manufactured by Clariant), 10 parts by mass of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by mass of ion-exchanged water are mixed. Using a high-pressure impact disperser Ultimizer (HJP30006: manufactured by Sugino Machine Co., Ltd.), the mixture was dispersed for 1 hour to obtain a magenta colorant dispersion.

  When the volume average particle diameter of the colorant (magenta pigment) in the obtained magenta colorant dispersion was measured using a laser diffraction particle size measuring instrument according to the measurement method described above, the volume average particle diameter was 168 nm. . The solid content ratio of the magenta colorant dispersion was 23.8% by weight.

-Preparation of black colorant dispersion-
Carbon black Regal 330: 100 parts by mass (manufactured by Cabot), 10 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by mass of ion-exchanged water are mixed, and high-pressure impact dispersion A black colorant dispersion was obtained by dispersing for 1 hour using a machine optimizer (HJP30006: manufactured by Sugino Machine Co., Ltd.).

  When the volume average particle size of the colorant (carbon black) in the obtained black colorant dispersion was measured using a laser diffraction particle size measuring instrument by the above-described measurement method, the volume average particle size was 228 nm. . The solid content ratio of the black colorant dispersion was 23.2% by weight.

[Preparation of release agent dispersion (1)]
FT100 (Nippon Seiki): 400 parts by mass After the above components were heated to 120 ° C. and mixed,
Neogen SC (Daiichi Kogyo Seiyaku): 20 parts by mass were added.
Ion-exchanged water: placed in 1600 parts by mass and dispersed with a pressure discharge type homogenizer with a pressure of 120 ° C. and a pressure of 50 MPa to prepare a release agent dispersion liquid (1) (solid content concentration: 20%).

<Production of toner>
[Example 1]
Ion-exchanged water: 450 parts by weight Polymer polyester resin dispersion (1): 220 parts by weight Low molecular weight polyester resin dispersion (1): 147 parts by weight Anionic surfactant: 2.8 parts by weight (Daiichi Kogyo Seiyaku ( Co., Ltd .: Neogen RK, 20% by mass)
Was placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside.
Cyan colorant dispersion: 60 parts by weight Release agent dispersion (1): 100 parts by weight was added and held for 5 minutes. The 1.0 wt% nitric acid aqueous solution was added as it was, and the pH in the aggregation process was adjusted to 5.5.

  While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the temperature was raised to 50 ° C. while stirring, and the particle size was measured. Was 5.5 μm. Thereafter, 110 parts by mass of the high-molecular polyester resin dispersion (1) and 73 parts by mass of the low-molecular polyester resin dispersion (1) were added, and the resin particles were adhered to the surface of the aggregated particles.

  Thereafter, the pH was adjusted to 9.0 using a 5% by mass aqueous sodium hydroxide solution. Thereafter, the temperature was increased to 90 ° C. at a rate of temperature increase of 0.05 ° C./min, held at 90 ° C. for 3 hours, cooled, filtered, redispersed with ion-exchanged water, filtered, filtrated. The toner was repeatedly washed until the electric conductivity of the toner became 20 μS / cm or less, and then vacuum-dried in an oven at 40 ° C. for 5 hours to obtain a toner.

  A sample containing 1.5 parts by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 1.0 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) with respect to 100 parts by mass of the obtained toner. The blend was blended for 30 seconds at 10,000 rpm using a mill. Thereafter, the toner (1) was prepared by sieving with a vibration sieve having an opening of 45 μm. The toner (1) obtained had a volume average particle diameter of 6.1 μm. Further, when classification was performed with an elbow jet at a cut point of 4 μm, the volume average particle diameter on the fine powder side was 2.8 μm, and the molecular weight on the fine powder side and the total molecular weight of the toner were (MwS / MwT) × 100 = 170. Met.

[Example 2]
Toner (2) was prepared according to Example 1 except that the low molecular weight polyester resin dispersion (1) was replaced with the low molecular weight polyester resin dispersion (2) instead of the low molecular weight polyester resin dispersion (1). The obtained toner (2) was (MwS / MwT) × 100 = 150.

[Example 3]
Toner (3) was prepared according to Example 1, except that the low molecular weight polyester resin dispersion (1) was replaced by the low molecular weight polyester resin dispersion (3) instead of the low molecular weight polyester resin dispersion (1). The obtained toner (3) was (MwS / MwT) × 100 = 200.

[Example 4]
Toner (4) was prepared according to Example 1, except that the black colorant dispersion was used instead of the cyan colorant dispersion. The obtained toner (4) was (MwS / MwT) × 100 = 165.

[Example 5]
Toner (5) was prepared according to Example 1 except that a yellow colorant dispersion was used instead of the cyan colorant dispersion. The obtained toner (5) was (MwS / MwT) × 100 = 170.

[Example 6]
Toner (6) was prepared according to Example 1 except that a magenta colorant dispersion was used instead of the cyan colorant dispersion. The obtained toner (6) was (MwS / MwT) × 100 = 180.

[Comparative Example 1]
A polymer polyester resin dispersion (2) was obtained by setting the emulsification conditions of the amorphous polyester resin (1) described above to 0.5 parts of estimated sodium oxide. The coagulation value of the polymer polyester resin dispersion (2) was 5.3 × 10 ⁻⁶ . Then, a toner (7) was prepared according to Example 1 except that the polymer polyester resin dispersion (2) dispersion was used instead of the polymer polyester resin dispersion (1). The obtained toner (7) was (MwS / MwT) × 100 = 90.

[Comparative Example 2]
Toner (8) was prepared in the same manner as in Example 3 except that the pH was 6.2 at the aggregation step. The obtained toner (8) was (MwS / MwT) × 100 = 230.

[Comparative Example 3]
Toner (7) was prepared in the same manner as in Example 1 except that the aggregation step was performed at pH 4.2. The obtained toner (9) was (MwS / MwT) × 100 = 105, and there was no molecular weight uneven distribution.

-Preparation of metallic glossy toner-
[Example 7]
A gold foil having a thickness of 4 nm is spray-coated with polypropylene wax (crystallinity 60, melting point 68 ° C.), dispersed in an aqueous solvent composed of acetone and ion-exchanged water, pulverized by a bead mill, and a gold foil having a longitudinal direction of 650 nm. Pigment (1) was produced.

Gold foil pigment dispersion (1) (solid content 24%): 200 parts by weight Release agent dispersion (1) (solid content 45%, release agent crystallinity 80): 100 parts by weight Cationic surfactant ( Sanisol B50, manufactured by Kao Corporation): 3 parts by mass Ion-exchanged water: 500 parts by mass The above components were heated from a jacket to 42 ° C. in a 3 L agitation tank, and held at 42 ° C. for 1 hour. As a result, aggregated particles were formed. When a part of the obtained aggregated particles was observed with an optical microscope, the average particle size of the aggregated particles was about 2.3 μm.

  Next, 6 parts by weight of anionic surfactant sodium dodecylbenzenesulfonate (Daiichi Kogyo Co., Ltd .: Neogen SC) was added to this dispersion, heated and held at 63 ° C. for 3 hours to fuse the particles, and then 10 ° C. 700 parts by mass of ion-exchanged water, cooled to 50 ° C. in 1.5 minutes, filtered, thoroughly washed with ion-exchanged water, filtered through a 400 mesh sieve, and colored release agent particles (1) Got. The average particle diameter of the obtained particles was 2.4 μm.

Colored release agent particle dispersion (1) (solid content: 36%): 100 parts by weight High-molecular polyester resin dispersion (1): 220 parts by weight Low-molecular polyester resin dispersion (1): 167 parts by weight Cationic interface Activator (manufactured by Kao Corporation: Sanizol B50): 3 parts by mass Ion-exchanged water: 450 parts by mass The above components are placed in a 3 L reaction vessel equipped with a thermometer, pH meter, and stirrer, and the temperature is controlled from the outside with a mantle heater. While maintaining at a temperature of 30 ° C. and a stirring speed of 150 rpm, the temperature was maintained for 30 minutes. Thereafter, a 1.0 wt% aqueous nitric acid solution was added to adjust the pH in the aggregation step to 5.5.

  While adding 0.4 parts by mass of polyaluminum chloride while dispersing with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax T50), the mixture is heated to 55 ° C. while stirring from the jacket, and held at 55 ° C. for 1 hour to aggregate particles Formed. When the particle size was measured with a Coulter counter [TA-II] type (aperture diameter: 50 μm, manufactured by Coulter, Inc.), the average particle size of the aggregated particles was about 7.2 μm.

  Thereafter, 110 parts by mass of the high-molecular polyester resin dispersion (1) and 73 parts by mass of the low-molecular polyester resin dispersion (1) were added, and the resin particles were adhered to the surface of the aggregated particles.

  Next, 6 parts of anionic surfactant sodium dodecylbenzenesulfonate (Daiichi Kogyo Co., Ltd .: Neogen SC) was added to this dispersion, heated to 92 ° C., held at 92 ° C. for 5 hours, and aggregated particles Fused. Thereafter, cooling, filtration, redispersion with ion-exchanged water, filtration, washing repeatedly until the electric conductivity of the filtrate is 20 μS / cm or less, and then vacuum in an oven at 40 ° C. for 5 hours. The toner (10) was obtained by drying.

  To 100 parts by mass of the obtained toner (10), 3.3 parts by mass of colloidal silica (manufactured by Nippon Aerosil Co., Ltd .: R972) is added and mixed using a Henschel mixer to obtain the electrostatic charge developing toner (10). Obtained. The obtained toner (10) was (MwS / MwT) × 100 = 170. When the metallic gloss was evaluated, the light receiving angle width was 5 ° or more, which was good. Further, when the charge amount was measured, it was 34 μC / g, and the chargeability was also good.

[Example 8]
A gold foil having a film thickness of 1 nm is spray-coated with polypropylene wax (crystallinity 60, melting point 68 ° C.), dispersed in an aqueous solvent composed of acetone and ion-exchanged water, pulverized by a bead mill, and a gold foil having a longitudinal direction of 100 nm. Pigment (2) was prepared.

  Toner (11) was prepared according to Example 7 except that the gold foil pigment (2) was used instead of the gold foil pigment (1). The obtained toner (11) was (MwS / MwT) × 100 = 170. When the metallic gloss was evaluated, the light receiving angle width was 5 ° or more, which was good. Further, when the charge amount was measured, it was 36 μC / g, and the chargeability was also good.

[Example 9]
A gold foil with a thickness of 9 nm is spray-coated with polypropylene wax (crystallinity 60, melting point 68 ° C.), then dispersed in an aqueous solvent composed of acetone and ion-exchanged water, pulverized by a bead mill, and a gold foil having a longitudinal direction of 1500 nm. Pigment (3) was prepared.

  A toner (12) was prepared according to Example 7 except that the gold foil pigment (3) was used instead of the gold foil pigment (1). The obtained toner (12) was (MwS / MwT) × 100 = 170. When the metallic gloss was evaluated, the light receiving angle width was 5 ° or more, which was good. Further, when the charge amount was measured, it was 31 μC / g, and the chargeability was also good.

[Comparative Example 4]
A gold foil having a film thickness of 10 nm is spray-coated with polypropylene wax (crystallinity 60, melting point 68 ° C.), dispersed in an aqueous solvent composed of acetone and ion-exchanged water, pulverized by a bead mill, and a gold foil having a longitudinal direction of 70 nm. Pigment (4) was prepared.

  Toner (13) was prepared in the same manner as in Example 7 except that the above gold foil pigment (4) was used instead of the gold foil pigment (1). The obtained toner (13) was (MwS / MwT) × 100 = 175. When the metallic gloss was evaluated, the light receiving angle width was less than 4.5 °, and there was no metallic gloss. Further, when the charge amount was measured, it was 35 μC / g, and the chargeability was good.

[Comparative Example 5]
A gold foil having a film thickness of 10 nm is spray-coated with polypropylene wax (crystallinity 60, melting point 68 ° C.), then dispersed in an aqueous solvent composed of acetone and ion-exchanged water, pulverized by a bead mill, and a gold foil having a longitudinal direction of 1800 nm. Pigment (5) was prepared.

  Toner (14) was prepared according to Example 7, except that the above-mentioned gold foil pigment (5) was used instead of the gold foil pigment (1). The obtained toner (14) was (MwS / MwT) × 100 = 165. When the metallic gloss was evaluated, the light receiving angle width was 5 ° or more, which was good. However, when the charge amount was measured, it was 3 μC / g, and there was a problem in chargeability.

[Carrier adjustment]
Ferrite particles (average particle size: 50 μm): 100 parts by mass Toluene: 14 parts by mass Styrene / methyl methacrylate copolymer (copolymerization ratio: 15/85): 2 parts by mass Carbon black: 0.2 parts by mass First, ferrite particles The above components except for the above were dispersed in a sand mill, and the dispersion was put into a vacuum degassing type kneader with ferrite particles, and dried under reduced pressure while stirring to obtain a carrier. The volume average particle size distribution index GSDv of the carrier was 1.20.

[Developer preparation]
To 100 parts of the carrier, 8 parts of the toners of Examples and Comparative Examples were mixed to obtain developers of Examples and Comparative Examples.

<Evaluation method>
[Evaluation of high-temperature fixability]
(Evaluation of offset property)
The obtained developer is filled in a developing unit of a DocuCentreColor400CP remodeling machine (manufactured by Fuji Xerox Co., Ltd., which can arbitrarily set a fixing temperature and a process speed) shown in FIG. The image is fixed so that the temperature range is 5 ° C., and the obtained image has a constant shot density (paper C2, paper made by Fuji Xerox Co., Ltd., density 1.5 to 1.8 with an X-Rite 404 densitometer). An image defect caused by bending the image thus obtained was subjected to sensory evaluation and judged according to the following criteria. The process speed was implemented at three levels of 160 mm / s, 250 mm / s, and 370 mm / s. The evaluation criteria are shown below.
A: No problem at 190 ° C. or higher at any process speed and image density (not visually recognized as image defects).
A: Some image defects are observed at a process speed of 370 mm / s and 190 ° C. (no problem in actual use).
Δ: No problem in practical use, but image defects are observed at a high image density and high temperature part (170 ° C. or higher and 190 ° C. or lower).
X: Many image defects in the high temperature part (170 ° C. or more and 190 ° C. or less), and in a temperature range that cannot be practically used (fixed at 170 ° C. or less and no image defects are observed).

[Evaluation of cleaning properties]
(Image quality fog evaluation)
The developer obtained in an environmental chamber at a room temperature of 32 ° C. and a humidity of 85% is set in the developer of the DocuCentreColor400CP modified machine manufactured by Fuji Xerox Co., Ltd. shown in FIG. 2, and continuously 20000 sheets at a process speed of 250 mm / s. Was printed out. Each time 10,000 sheets were printed out, the surface of the photoreceptor was visually confirmed and evaluated according to the following criteria.
A: No photoconductor contamination due to toner collapse up to 20000 sheets. O: No photoconductor contamination due to toner collapse up to 10,000 sheets.
X: On 10,000 sheets, there is obvious contamination of the photoreceptor due to toner crushing.

[Metal gloss]
Using the obtained developer A, a DocuCentreColor400CP remodeling machine (fixing machine configuration: heat roll and belt, nip width: 16 mm) was adjusted so that the toner mass per unit area was 18.0 mg / cm ² , and Jcoat paper A toner image of 3.5 mg / cm ^{2 was} formed on Fuji Xerox Office Supply Co., Ltd., and fixing was performed by adjusting the fixing temperature to 180 ° C. and the process speed to 80 mm / second. The obtained golden fixed image was measured using a GP200 model manufactured by Murakami Color Research Laboratory with an incident angle of 45 ° and a detection angle of 40 ° to 80 ° in steps of 0.1 °. Judgment criteria are shown below.
◯: The light receiving angle width of 90% or higher at 45 ° and the light receiving angle width of 1% or higher is 5 ° or higher. Δ: The light receiving angle width of 45% or higher at 45 ° and 1% or higher is 4%. .5 ° or more ×: Those that do not satisfy the above conditions

[Charging characteristics]
The obtained developer (1) was charged in a developer of a modified DocuCenter Color 500 (Fuji Xerox Co., Ltd.) and left for 24 hours in an environment of 28 ° C./85% RH. Thereafter, the developing device was idled for 3 minutes in the adjusting mode of the developing device, and then the developer was collected from the developing sleeve, and the charge amount of the toner was measured using a blow-off charge amount measuring device (TB200, manufactured by Toshiba Corporation). . The evaluation criteria are shown below. The results are shown in Table 2.
○: 30 μC / g or more and less than 50 μC / g,
Δ: 10 μC / g or more and less than 30 μC / g,
X: Less than 10 μC / g.

  The electrostatic charge developing toner of the present invention is particularly useful for uses such as electrophotography and electrostatic recording.

1 is a schematic diagram illustrating a configuration example of an image forming apparatus used in the present embodiment. FIG.

Explanation of symbols

  200 Image forming apparatus, 400 housing, 401, 401a to 401d electrophotographic photosensitive member, 402, 402a to 402d charging roll, 403 exposure apparatus, 404, 404a to 404d developing apparatus, 405a to 405d toner cartridge, 409 intermediate transfer belt, 410 , 410a to 410d Primary transfer roll, 411 tray (transfer medium tray), 413 Secondary transfer roll, 414 Fixing roll, 415a to 415d, 416 Cleaning blade, 500 Transfer medium.

Claims (10)

Contains two or more binder resins, a colorant, and a release agent. The volume average particle diameter of the entire toner is D50T, the weight average molecular weight of the toner is MwT, and the toner is classified to give a volume average particle diameter of (1 / 5) MwT and MwS satisfy the relationship of the following formula (1), where MwS is the weight average molecular weight of the toner in the range of not less than D50T and not more than (2/3) × D50T. Developing toner.
150 ≦ (MwS / MwT) × 100 ≦ 200 (1)   2. The electrostatic charge developing toner according to claim 1, wherein the binder resin is a polyester resin.   2. The electrostatic charge developing toner according to claim 1, wherein a small particle size side number particle size distribution index GSDp-under is in a range of 1.15 to 1.30.   The colorant is a metal foil having a film thickness of 1 nm or more and 10 nm or less and a longitudinal direction of 80 nm or more and 1500 nm or less, and exhibits a metallic luster after transfer. Toner for electrostatic charge development.   5. The electrostatic charge developing toner according to claim 4, wherein the surface of the metal foil is coated with a resin compatible with a release agent, and the crystallinity of the release agent is 80 or more.   6. The electrostatic charge developing toner according to claim 4, wherein the metal foil is any one of gold, silver, and copper.   It contains the toner for electrostatic charge development according to any one of claims 1 to 6 and a carrier whose volume average particle size distribution index GSDv is in the range of 1.15 to 1.35. Developer for developing electrostatic charge.   A toner cartridge containing at least toner, wherein the toner is the electrostatic charge developing toner according to any one of claims 1 to 6.   A process cartridge comprising at least a developer holder and containing the developer for developing an electrostatic charge according to claim 7.   A latent image holding member, developing means for developing the electrostatic charge formed on the latent image holding member as a toner image with a developer, and transferring the toner image formed on the latent image holding member onto the transfer target. A transfer unit; a fixing unit that fixes the toner image transferred onto the transfer target; and a cleaning unit that cleans a transfer residual component by rubbing the latent image holding member with a cleaning member. An image forming apparatus comprising the electrostatic charge developing developer according to claim 7.

Images