JP2009092822A - Electrostatic charge developing toner, developer for electrostatic charge development, cartridge, manufacturing method for electrostatic charge developing toner, and image forming device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide electrostatic charge developing toner having a mechanical strength and durability. <P>SOLUTION: This electrostatic charge developing toner contains a binding resin, a coloring agent and a mold release agent, and has sea-island structure where the mold release agent exists as an island in the binding resin of a sea, a domain of the mold release agent contains fiber, and the binding resin contains 0.05 pts.mass or more to 5 pts.mass or less of inorganic particle having 5-200 nm of center particle size. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

  In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, an electrostatic latent image is developed with a developer containing toner to form a toner image, and the toner image is transferred to a recording medium. Fix and 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, the untransferred toner remaining after the transfer may be deformed or crushed by being rubbed by, for example, a rubber elastic blade in the cleaning process of the image forming apparatus. Therefore, in order to reinforce the strength of the toner, a method of coating inorganic particles on the surface of the toner particles and a method of externally adding inorganic particles to the toner particles have been proposed (for example, Patent Documents 1 and 2). Patent Document 3 contains a resin mainly composed of a cosmetic polyester and an amorphous polyester and / or an amorphous polyesteramide as a binder resin, and the amorphous polyester and / or the amorphous polyester. An electrophotographic toner is disclosed that contains a polycondensation product obtained by polycondensation of polyesteramide with terephthalic acid as a monomer and a polycondensation polymer obtained by polycondensation with fumaric acid as a monomer.

  However, in any of the methods, it is difficult to sufficiently suppress the deformation and crushing of the toner, and the durability of the toner required for reusing the transfer residual toner is not yet sufficient.

  Further, when an image is formed, when the thick paper and the thin paper are fixed by the same fixing device, the pressure received when passing through the fixing device differs depending on the thickness of the recording medium. Thick paper is subjected to high pressure, and thin paper is subjected to low pressure. At this time, the pressure applied to the toner on the paper is the same, and a difference appears in the image after fixing. In recent years, oilless fixing in which oil is removed from a fixing device is becoming mainstream from the viewpoint of long-term reliability and environment. As means for achieving oilless fixing from toner, means for enclosing a release agent in the toner has been proposed (for example, Patent Document 4). By this method, although the influence of the fixing pressure on the releasability is mitigated, the amount of the release agent exuded by the pressure changes and the gloss of the image changes. In addition, when a large amount of release agent is added, the binder component and the release agent exhibit compatibility, and the exudation of the release agent cannot be performed stably and uniformly, so that the stability of peeling can be obtained. I can't. Moreover, the method of prescribing | releasing and improving the component of a mold release agent is proposed (for example, patent document 5, 6). Here, it is proposed that polyester-based wax is used to exert a releasing ability at a low temperature and that the fixing property is improved by defining a normal paraffin ratio and a DSC endothermic curve. In the method using paraffin wax described in Patent Document 6, the amount of addition can be reduced because the wax easily oozes out during fixing because of its weak affinity with the toner resin. This makes it possible to reduce the change in glossiness of the image due to the fixing pressure, but a low viscosity at the time of melting is necessary to satisfy the fixing performance with a small amount of wax, and the viscosity is not affected by the fixing pressure. It is difficult to follow, and sufficient improvement cannot be obtained.

  It has been proposed to contain a fibrous material as a method for increasing the strength of the toner itself. However, this method has no effect on the pressure during fixing and is difficult to improve.

JP-A-10-26842 JP-A-7-2614 JP 2001-175028 A JP-A-5-61239 JP-A-10-123903 JP 2000-321815 A JP 2006-305982 A

  The main object of the present invention is to improve the storability and durability of toner particles, and to provide an electrostatic charge developing toner having a stable image density and excellent image stability, an electrostatic charge developing developer, and a cartridge. Another object of the present invention is to provide an electrostatic charge developing toner manufacturing method and an image forming apparatus.

  The present invention is as follows.

  (1) A toner having a sea-island structure including a binder resin, a colorant, and a release agent, wherein the release resin is an island when the binder resin is the sea, and the release agent domain In the toner for developing an electrostatic charge image, fibers are contained, and the binder resin contains 0.05 to 5 parts by mass of inorganic particles having a center particle diameter of 5 to 200 nm. is there.

  (2) The electrostatic image developing toner according to (1), wherein the fibers contained in the release agent are present at random, and the inorganic particles are hydrophobic silica. is there.

  (3) The electrostatic image developing toner according to (1) or (2), wherein the release agent has a melt viscosity at 120 ° C. of 1 mPa · s to 10 mPa · s. It is.

  (4) In the electrostatic image developing toner according to any one of (1) to (3), the binder resin is an amorphous polyester resin, and the polyester resin and inorganic particles are used as a good solvent. Toner for developing an electrostatic charge image, which is an amorphous polyester resin derived from a polyester resin emulsified dispersion obtained by dissolving in a mixed solution of water and a water-soluble poor solvent, neutralizing it with ammonia, and then dropping water to effect phase inversion. It is.

  (5) In the electrostatic image developing toner according to any one of (1) to (3), the binder resin is an electrostatic image developing toner containing a crystalline resin.

  (6) An electrostatic charge image developing developer containing the electrostatic charge developing toner according to any one of (1) to (5) above and a carrier.

  (7) A latent image forming unit that forms a latent image on the latent image holding member, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and a transfer of the developed image onto the transfer target. A detachable cartridge having a transfer means for transferring, wherein the electrostatic charge developing developer includes the electrostatic charge developing toner according to any one of (1) to (5).

  (8) A resin particle dispersion in which amorphous polyester resin particles containing 0.05 to 5 parts by mass of inorganic particles having a center particle diameter of 5 to 200 nm are dispersed, and colorant particles are dispersed. Mixing a colorant particle dispersion, a release agent particle dispersion in which fibers and release agent particles are dispersed, and aggregating particles containing the resin particles, inorganic particles, colorant particles, release agent particles, and fibers. Agglomeration step to be formed, a step of adjusting the pH in the agglomeration system to stop the agglomeration growth, and heating the agglomerated particles to a temperature above the glass transition temperature or melting point of the resin fine particles to fuse and coalesce toner particles. Forming the toner for electrostatic charge development.

  (9) In the method for producing a toner for developing an electrostatic image according to (5), the resin particle dispersion is obtained by dissolving an amorphous polyester resin in a mixture of a good solvent and a water-soluble poor solvent. This is a method for producing a toner for developing an electrostatic charge image, using an amorphous polyester resin emulsion dispersion obtained by neutralizing water with ammonia and then dropping water to effect phase inversion emulsification.

  (10) A latent image forming means for forming a latent image on the latent image carrier, a developing means for developing the latent image using an electrostatic charge developing developer, and the developed toner image via an intermediate transfer member Alternatively, the image forming apparatus includes: a transfer unit that transfers the toner image on the transfer body without being interposed; and a fixing unit that adds and fixes the toner image on the transfer body. An image forming apparatus which is the developer for electrostatic charge development described in 6).

  According to the present invention, the inorganic particles contained in the binder resin in the toner and the fibers contained in the release agent each have a filler effect, so that the mechanical strength of the toner compared to the conventional electrostatic charge developing toner. And the durability of the toner is improved. As a result, even when a mechanical load is applied to the toner, the toner itself does not crush or agglomerate, the toner maintains fluidity and chargeability, the image density is stable, and the image stability is excellent. It is possible to provide a toner for developing an electrostatic charge, a developer for developing an electrostatic charge, a cartridge, a method for producing the toner for developing an electrostatic charge, and an image forming apparatus.

<Toner for electrostatic charge development>
The electrostatic charge developing toner of the present embodiment (hereinafter sometimes abbreviated as “toner”) includes a binder resin, a colorant, and a release agent. When the binder resin is the sea, the release agent is The toner has a sea-island structure such as an island, wherein the release agent domain includes fibers, and the binder resin contains inorganic particles having a center particle size of 5 nm or more and 200 nm or less. It is contained in an amount of 05 parts by mass or more and 5 parts by mass or less.

[Inorganic particles]
As the inorganic particles, the inorganic particles used in the invention are silica, hydrophobized silica, titanium oxide, alumina, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, alumina-treated colloidal silica, and cation surface-treated colloidal silica. And anion surface-treated colloidal silica.

  The center particle diameter of the inorganic particles is used in the range of 5 nm to 200 nm as described above. When the center particle size of the inorganic particles is less than 5 nm, the glossiness of the image can be obtained, but the toughness (mechanical strength) of the resin is insufficient, and it becomes difficult to improve the toner strength. If the thickness exceeds 200 nm, the mechanical strength of the toner can be obtained, but the viscosity at the time of fixing becomes large, the fluidity is lowered, and the smoothness and glossiness of the image are lowered. A preferred central particle size range of the inorganic particles is 10 nm or more and 150 nm or less, and a more preferred range is 20 nm or more and 100 nm or less.

  The amount of inorganic particles added to the binder resin is 0.05 parts by mass or more and 5.0 parts by mass or less as described above. When the amount of inorganic particles added is less than 0.05 parts by mass, if the amount is too small, the effect of adding inorganic particles cannot be obtained, and specifically, the mechanical strength of the toner cannot be obtained. The improvement effect cannot be obtained. On the other hand, if it exceeds 5.0 parts by mass, the fluidity at the time of melting the toner is greatly reduced, the image glossiness is impaired, and the fixing performance is deteriorated. Specifically, the adhesion to the transfer paper is lowered, and as a result, it is not possible to ensure the folding durability of the fixed image. The preferable range of the addition amount of the inorganic particles is 0.5 parts by mass or more and 3.0 parts by mass or less, more preferably 1.0 part by mass or more and 2.5 parts by mass or less.

[Release agent and fiber]
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. Further, the release agent in the toner has better release properties when the domain is formed. If the mold release agent is a low melt viscosity wax, the mold release property is higher and the effect is obtained in a small amount. However, the pressure at the time of fixing affects the amount of oozing out of the wax, and changes the gloss of the image. This is more pronounced for low melt viscosity waxes.

  Accordingly, when fibers are contained in the release agent domain, it becomes difficult to be affected by the fixing pressure, and a good image can be obtained. The reason is not clear, but it is considered to control the viscosity of the wax with respect to pressure by the presence of fibers when the release agent is melted. In addition, if the fibers are present at random, the effect is further improved. This is considered to be because the effect is obtained by preventing the wax from flowing out in a certain direction.

  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 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.

  Although the fiber used for embodiment of this invention is not specifically limited, It is preferable that it is nano size. A preferable range is a fiber diameter of 1 nm to 300 nm, and more preferably 10 nm to 100 nm. Within this range, it is preferable to easily control the melt viscosity of the wax during fixing. Compositions include carbon fibers such as carbon nanofibers and carbon nanotubes, nanofibers composed of silicon carbide, nanofibrous materials composed of inorganic oxides such as titanium oxide and silicon oxide, polymers such as lactic acid, cellulose, amide, imide, and vinyl. Nano-fibrous material made of wood, natural products such as wood chips, cotton, hemp, etc. Preferably, a nanofibrous material made of carbon fiber or polymer in which the fiber does not become granular is preferable.

  The addition amount of the fiber is preferably in the range of 0.5 parts by mass or more and 5.0 parts by mass or less, and in the range of 1.0 part by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the wax. More preferably, it is within. Within this range, it is preferable to easily control the melt viscosity of the wax during fixing.

  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 the amorphous polyester is not particularly limited, as with the method for producing the crystalline polyester described above, 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 mentioned for the crystalline polyester can be used similarly. As the alcohol (diol) component, various diols used for the synthesis of the amorphous polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester, bisphenol A and bisphenol A ethylene oxide adducts are used. Bisphenol A propylene oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, etc. can be used, but from the viewpoint of toner productivity, heat resistance and transparency, It is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct. 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.

  In addition, similar to the crystalline polyester described later, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring, etc. can be used for the purpose of adjusting the melting point and molecular weight of the amorphous polyester. The various dicarboxylic acids and diols mentioned in the above can be used.

  Similar to the crystalline polyester described later, when a monofunctional monomer is introduced into the amorphous polyester for the purpose of blocking the polar group at the end of the amorphous polyester and improving the environmental stability of the toner charging characteristics. There is. As the monofunctional monomer, various compounds mentioned for the crystalline polyester can be used.

  As the other binder resin for forming the toner used in the embodiment of the present invention, a known one can be used. Although not particularly limited, for example, styrene resin, acrylic resin, styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, polyolefin resin, a mixture thereof, or the presence thereof And graft polymers obtained by polymerizing vinyl monomers.

  Preferred other binder resins are styrene-acrylic resins and polyester resins, and particularly preferably a mixture of a crystalline polyester resin and an amorphous polyester resin. A mixture of crystalline polyester resin and amorphous polyester resin enables low-temperature fixing by lowering the viscosity of the crystalline polyester resin at the time of fixing, and the amorphous polyester resin improves image strength, resulting in good performance. Is obtained.

-Styrenic resin-
Examples of the styrene resin include the above-described polystyrene, styrene butadiene polymer, and styrene acrylic polymer. These can be produced using the following monomers.

  Examples of styrene monomers include styrene, α-methyl styrene, vinyl naphthalene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2-ethyl styrene, 3-ethyl styrene, 4-ethyl styrene, and the like. Examples include alkyl-substituted styrene having an alkyl chain, halogen-substituted styrene such as 2-chlorostyrene, 3-chlorostyrene, and 4-chlorostyrene, and fluorine-substituted styrene such as 4-fluorostyrene and 2,5-difluorostyrene. Styrene is preferred as the styrene monomer.

  Examples of the (meth) acrylate monomer include n-methyl (meth) acrylate, n-ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, ( N-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n (meth) acrylate -Dodecyl, n-lauryl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate, n-octadecyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acryl Isobutyl acid, t-butyl (meth) acrylate, isopentyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Pentyl, isohexyl (meth) acrylate, isoheptyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, biphenyl (meth) acrylate, (meth) acryl Diphenylethyl acid, t-butylphenyl (meth) acrylate, terphenyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (meth ) Diethylaminoethyl acrylate, methoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid-β-carboxyethyl, (meth) acrylonitrile, (meth) acrylamide and the like. As the (meth) acrylic acid ester monomer, n-butyl acrylate is preferable.

  When the styrene resin, the (meth) acrylic resin and the styrene- (meth) acrylic copolymer resin contain a carboxyl group, it can be obtained by copolymerizing a polymerizable monomer having a carboxyl group. .

  Specific examples of such a carboxyl group-containing polymerizable monomer include acrylic acid, aconitic acid, atropic acid, allylmalonic acid, angelic acid, isocrotonic acid, itaconic acid, 10-undecenoic acid, elaidic acid, erucic acid, olein. Acid, ortho-carboxycinnamic acid, crotonic acid, chloroacrylic acid, chloroisocrotonic acid, chlorocrotonic acid, chlorofumaric acid, chloromaleic acid, cinnamic acid, cyclohexenedicarboxylic acid, citraconic acid, hydroxycinnamic acid, dihydroxysilicic acid Cinnamic acid, tiglic acid, nitrocinnamic acid, vinyl acetic acid, phenyl cinnamic acid, 4-phenyl-3-butenoic acid, ferulic acid, fumaric acid, brassic acid, 2- (2-furyl) acrylic acid, bromocinnamic acid, Bromofumaric acid, bromomaleic acid, benzylidene malonic acid, benzo Acrylic acid, 4-pentenoic acid, maleic acid, mesaconic acid, methacrylic acid, methylcinnamic acid, methoxycinnamic acid, etc., and acrylic acid, methacrylic acid, maleic acid, cinnamic acid due to the ease of polymer formation reaction, etc. , Fumaric acid and the like are preferable, and acrylic acid is more preferable.

  A chain transfer agent can be used during the polymerization of the binder resin used for the toner particles in the toner set of the present embodiment. Although there is no restriction | limiting in particular as a chain transfer agent, The compound which has a thiol component can be used. Specifically, alkyl mercaptans such as hexyl mercaptan, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan, and dodecyl mercaptan are preferred, and in particular, the molecular weight distribution is narrow, so that the storage stability of the toner at high temperature is improved. preferable.

  Among the binder resins used for the toner particles in the toner set of the present invention, those that can be produced by radical polymerization of a polymerizable monomer can be polymerized using a radical polymerization initiator.

  There is no restriction | limiting in particular as an initiator for radical polymerization used here. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, tert-butyl hydroperoxide pertriphenyl acetate, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobisp Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Sodium methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihy Roxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis-4 -Dimethyl cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'- Azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1 ′ -Azobiscumene, 4-nitrophenylazobenzyl cyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmeth Tan, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol) -2,2'-azobisisobutyrate) and the like, 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like Can be mentioned.

-Crystalline polyester resin-
The crystalline polyester resin in the present invention will be described below. The “crystalline walk ester resin” refers to a resin having a clear endothermic peak in differential scanning calorimetry (DSC). “Crystallinity” used in the toner for developing an electrostatic charge of the present invention means that it has a clear endothermic peak in differential scanning calorimetry (DSC), specifically, at a heating rate of 10 ° C./min. It means that the half width of the endothermic peak when measured is within 6 ° C.

  A known crystalline polyester resin can be used as the crystalline polyester resin used in the binder resin of the present embodiment.

  A crystalline polyester resin has a melting point and thus has a large decrease in viscosity at a specific temperature. When the toner is heated at the time of fixing, the temperature difference from the start of the crystalline polyester molecule to thermal activity to the fixable region. Therefore, it is possible to impart further excellent low-temperature fixability. The preferred content of the crystalline polyester in the toner particles is in the range of 1 to 10% by mass, more preferably in the range of 2 to 8% by mass.

  Further, the number average molecular weight (Mn) of the crystalline polyester resin is preferably 2000 or more, and more preferably 4000 or more. If the number average molecular weight (Mn) is less than 2000, the toner may permeate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the bending strength of the fixed image may be reduced.

  The crystalline polyester is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. Hereinafter, the acid (dicarboxylic acid) component and the alcohol (diol) component will be described in more detail. In the present invention, a copolymer obtained by copolymerizing other components at a ratio of 50% by mass or less with respect to the main chain of the crystalline polyester is also referred to as a crystalline polyester.

  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 content of the acid (carboxylic acid component) of the acid (dicarboxylic acid) component other than these aliphatic dicarboxylic acid components (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group), 1 component mol% or more and 20 component mol% or less are preferable, and 2 component mol% or more and 10 component mol% or less are more preferable.

  When the content is less than 1 component mol%, the dispersibility of the pigment in the toner may not be good. Further, when a toner is produced using an aggregation / unification method, the emulsion particle size in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation.

  On the other hand, when it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting point is lowered, and the storage stability of the toner may be deteriorated. In addition, when a toner is produced using an agglomeration method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not occur. In the present invention, “constituent mol%” refers to a percentage when each constituent component [acid (carboxylic acid) component, alcohol (diol) component] in the polyester resin is 1 unit (mol).

  On the other hand, 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, , 14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like, but are not limited thereto.

  The alcohol (diol) component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol (diol) component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, toner storage stability and low-temperature fixability may be deteriorated.

  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.

  The method for producing the crystalline 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. Produced separately depending on the type of monomer. 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 crystalline 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 usable in the production of the crystalline polyester include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium Compound: Phosphorous acid compound, phosphoric acid compound, amine compound and the like are mentioned, and specifically, the following compounds are mentioned.

  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 above polymerizable monomers, compounds having shorter chain alkyl groups, alkenyl groups, aromatic rings and the like can also be used for the purpose of adjusting the melting point, molecular weight and the like of the crystalline 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 end of the crystalline polyester and improving the environmental stability of 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.

  The ratio of the amorphous resin to the crystalline resin is preferably in the range of 60/40 to 95/5, and particularly preferably in the range of 75/25 to 90/10. When the ratio of the amorphous resin is decreased, the strength of the toner itself is decreased, and blocking and filming are likely to occur. Further, when the crystalline resin is reduced, fixing at low temperature becomes difficult.

<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, induslen 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.

  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.

<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.

  An example of a toner manufacturing method in the present embodiment is a resin particle dispersion in which amorphous polyester resin particles containing 0.05 to 5 parts by mass of inorganic particles having a center particle diameter of 5 to 200 nm are dispersed. And a colorant particle dispersion liquid in which colorant particles are dispersed, and a release agent particle dispersion liquid in which fibers and release agent particles are dispersed, and the resin particles, inorganic particles, colorant particles, and release agent particles are mixed. Agglomeration step of forming agglomerated particles containing fibers and fibers, a step of adjusting the pH in the agglomerated system to stop agglomeration growth, and heating the agglomerated particles to a temperature above the glass transition temperature or the melting point of the resin fine particles for fusion And uniting them to form toner particles. By the above production method, when the binder resin is the sea, a toner having a sea-island structure in which the release agent is an island can be obtained, and the release agent can form a domain in the toner.

  As a method for preparing a toner containing fibers in a release agent, a release agent particle dispersion liquid in which fibers are contained in a release agent is prepared in advance, and this fiber-containing release agent particle dispersion liquid is prepared. This is possible by using the toner manufacturing method. When a toner is prepared by simply adding fibers in the above toner production method, the affinity between the resin and the fibers is higher than that of the release agent, and particularly when the release agent is a low-melting wax, it becomes more prominent. Fibers do not enter the mold. Further, when a resin, a release agent, a colorant, and a fiber are mixed by a kneading method, the release agent hardly forms a domain and may not contain a fiber.

  The release agent particle dispersion containing the fibers can be produced, for example, as follows. A mold release agent, fiber, and surfactant are added to a low boiling point solvent such as ethyl acetate or methyl ethyl ketone, heated to near the melting point of the mold release agent, and sheared by a homogenizer (IKA Japan: Ultra Tarax T50). . Continue shearing until the desired release agent particle size is reached, then add ion-exchanged water in an equivalent amount to the solvent, transfer the release agent particles to the water layer, and volatilize the solvent component. A dispersion containing fibers can be obtained. The fibers in the release agent thus prepared are easily aligned in the rotation direction of a homogenizer (manufactured by IKA Japan Co., Ltd .: Ultra Tarax T50) and have an orientation.

  In addition, as a method of randomly encapsulating the fibers in the release agent, the release agent, ion-exchanged water, surfactant, fibers are mixed, and from the melting point of the release agent by a discharge type disperser such as a gorin homogenizer. By dispersing at a temperature of 30 ° C. or higher, a release agent particle dispersion containing fibers randomly oriented in the release agent can be obtained.

  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.

  Next, each process in an example of the aggregation / unification method described above will be described 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.

  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.

  The agglomeration and coalescence method can also be performed by mixing and aggregating together. Specifically, for example, the balance of the ionic dispersant amount of each polarity is shifted in advance at the initial stage of the aggregation step. More specifically, for example, a polymer of at least one metal salt is ionically neutralized to form a first-stage host aggregate at a temperature lower than the glass transition temperature. After stabilization, as the second stage, a second stage addition resin particle dispersion treated with a dispersant having a polarity and amount so as to compensate for the balance deviation is added, and if necessary, the base aggregated particles or the first Slightly heated at a temperature lower than the glass transition temperature of the resin contained in the resin particles for the two-stage addition, and after stabilizing the temperature, the second-stage addition is performed by heating to a temperature higher than the glass transition temperature. This is a method in which the resin particles are united while being adhered to the surface of the base aggregated particles. Furthermore, the stepwise operation of aggregation may be repeated several times. This two-stage method is effective for improving the inclusion of the release agent and the colorant.

  The metal salt polymer is preferably a tetravalent aluminum salt polymer, or a mixture of a tetravalent aluminum salt polymer and a trivalent aluminum salt polymer, specifically, calcium nitrate. And a polymer of an inorganic metal salt such as polyaluminum chloride. The metal salt polymer is preferably added so that its concentration is 0.11 to 0.25% by weight based on the entire particle dispersion.

[Shell formation process]
A shell forming step may be provided as necessary. In the shell forming step, the surface of the core aggregated particles is formed by attaching resin fine particles to the surface of the core aggregated particles using a resin fine particle dispersion containing resin fine particles to form a coating layer (shell layer) having a desired thickness. Aggregated particles having a core / shell structure in which a shell layer is formed (core / shell aggregated particles) are obtained.

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

  Here, the volume average particle size of the resin fine particles, colorant fine particles, and release agent fine particles used in the aggregation step and the shell formation step is to facilitate adjustment of the toner diameter and the particle size distribution to desired values. It is preferable that it is 1 micrometer or less, and it is more preferable that it exists in the range of 100-300 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 toner is obtained by heating to the above temperature and fusing and coalescing.

  Here, the temperature equal to or higher than the glass transition temperature of the resin fine particles refers to a temperature equal to or higher than the glass transition temperature of the resin fine particles having the highest glass transition temperature.

[Other processes]
After completion of aggregation, fusion, coalescence, and acid washing, a desired toner is obtained through a solid-liquid separation process and a drying process. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.

<Developer for electrostatic charge development>
The developer for developing an electrostatic charge of the present embodiment is not particularly limited except that it contains the toner for developing an electrostatic latent image of the present embodiment described above, and can have an appropriate component composition depending on the purpose. . The electrostatic charge image developer of the present invention becomes a one-component electrostatic charge image developer when the electrostatic charge developing toner is used alone, and a two-component electrostatic charge image developer when used in combination with a carrier. Become.
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 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.

  As the developing devices 404a to 404d, a general developing device that develops the two-component electrostatic image developer in contact or non-contact with the developer can be used (developing step). Such a developing device is not particularly limited as long as a two-component electrostatic image 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 uses a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member and a developer carried on the developer carrying member, and is formed on the surface of the latent image holding member. A developing step of developing the electrostatic latent image formed to form a toner image, a transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a transfer to the surface of the transfer target And a fixing step for thermally fixing the toner image, 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 latent image (latent image forming step). Next, the toner particles are adhered to the electrostatic latent image in 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.

  The toner recycling means in the image forming apparatus of the present embodiment will be described with reference to FIG.

  The cleaning step is a step of removing residual toner remaining as a transfer residue on the surface of the latent electrostatic image bearing member after the transfer step. In this step, a blade, brush, roll or the like is directly brought into contact with the surface of the electrostatic latent image carrier as the cleaning blade 416 to remove toner, paper dust, dust, etc. adhering to the surface of the electrostatic latent image carrier. Can do.

  The most commonly employed method is a blade cleaning method in which a rubber blade such as polyurethane is pressed against an electrophotographic photosensitive member 401 serving as an electrostatic latent image carrier. On the other hand, a magnet is fixedly arranged inside, a rotatable cylindrical non-magnetic sleeve is provided on the outer periphery thereof, and a magnetic carrier system that collects toner by carrying a magnetic carrier on the sleeve surface, or a semiconductive Alternatively, an electrostatic brush method may be used in which a functional resin fiber or animal hair is rotatable in a roll shape, and a bias having a polarity opposite to that of the toner is applied to the roll to remove the toner.

  In the embodiment of the present invention, a blade cleaning method is preferably used to perform toner recycling.

  The image forming method of the present invention further includes a toner recycling step. The toner recycling step is a step of transferring the transfer residual toner collected by the cleaning blade 416 in the cleaning step to a developing device 404 having a developer carrier. The image forming method of the present invention including the toner recycling step can be carried out using an image forming apparatus such as a toner recycling system type copying machine, printer, or facsimile machine. The toner recycling means has a conveyance path 420 having a screw auger that conveys the collected toner, and the conveyance path 420 is a pipe-like connection between the cleaning blade 416 and the toner replenishing tank 422 and has a screw-like shape that rotates inside. The conveying member is provided.

  The transfer residual toner collected by the cleaning blade 416 is sent to the entrance of the transport path by the rotation of the screw auger, and is transported to the toner supply tank 422 through the transport path 420 by the rotation of the transport member. The cleaning blade 416 is a plate made of urethane rubber or the like, and the tip thereof is in contact with the surface of the photosensitive drum. Further, the toner supply tank 422 is connected to the developing device 404 via a toner supply filter 424 for supplying toner. Therefore, in the toner image forming unit shown in FIG. 2, the toner replenishment tank 422 contains newly replenished replenishment toner, and also the collected toner collected by the cleaning blade 416 through the toner recycling means.

  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 at the second temperature rise, which was obtained by lowering the temperature at 10 ° C / min, holding at 0 ° C for 5 minutes, and again raising the temperature from 0 ° C to 150 ° C at 10 ° C / min. Was Tg.

(Resin acid value)
The resin acid value was measured as follows. About 1 g of resin is precisely weighed and dissolved in 80 ml of tetrahydrofuran. Phenolphthalein was added as an indicator, titrated with a 0.1N KOH ethanol solution, and the end point was when the color lasted for 30 seconds. From the amount of 0.1N KOH ethanol solution used, the acid value (contained in 1 g of resin) The number of mg of KOH necessary to neutralize free fatty acids was calculated according to JIS K0070: 92).

(Measurement of fiber in release agent)
A toner cross section containing at least an amorphous polyester resin, a crystalline polyester resin, a release agent, and a colorant and stained with ruthenium is observed with a transmission electron microscope, and the obtained image is analyzed.

  The method for observing the cross-sectional structure of the toner is implemented by combining a generally known microtome section preparation and an electronic staining method. Specifically, the measurement was performed by the following method. The toner was embedded in an epoxy resin and sectioned to a thickness of 100 nm using an ultramicrotome apparatus (ULTRACUT UCT manufactured by LEICA) equipped with a diamond knife SK2045T (manufactured by Sumitomo Electric Industries, Ltd.). This section was exposed to ruthenium tetroxide vapor for oxidative staining, and the section after staining was observed with a scanning electron microscope (TEM) to confirm the structure in which the crystalline polyester resin was in contact with the release agent in the toner. . In the toner, the crystalline polyester resin and the release agent were judged from the contrast and shape. Further, those present in the form of rods or lumps were judged as release agents, and the linear crystals scattered around the release agent and in the amorphous polyester resin of the toner were judged as crystalline polyester resins. In contrast, a whiter contrast portion was determined as a release agent. Since the binder resin other than the release agent has many double bond portions and is dyed with ruthenium tetroxide, the release agent portion can be distinguished from the resin portion other than the release agent. That is, the release agent is dyed lightest by ruthenium dyeing, then the crystalline polyester resin is dyed, and the non-crystalline polyester resin is dyed most intensely. In addition, it adjusted so that the cross section of about 50 toner particles may be included in one section.

  The fibers contained in the release agent region are specified, and the degree of dispersion and the amount added are calculated.

[Preparation of polyester resin dispersion (1)]
Bisphenol A ethylene oxide 2-mol adduct: 30 mol%
Bisphenol A propylene oxide 2 mol adduct: 20 mol%
Terephthalic acid dimethyl ester: 32.5 mol%
Dodecenyl succinic acid: 15 mol%
Trimellitic acid: 2.5 mol%
The above monomer is charged into a 5 liter flask equipped with a stirrer, nitrogen inlet tube, temperature sensor, and rectifying column. The temperature is raised to 190 ° C. over 1 hour, and the reaction system is 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 40000, and a number average molecular weight of 6500 was obtained.

[Additional inorganic fine particles]
Inorganic fine particles A: R972 (hydrophobized silica manufactured by Nippon Aerosil Co., Ltd.); average particle size = 16 nm
Inorganic fine particle B: RY50 (manufactured by Nippon Hydrosil Hydrophobized silica); average particle size = 40 nm
Inorganic fine particles C: Silica sol obtained by the sol-gel method was treated with hexamethyldisilazane, and dried and pulverized to obtain hydrophobized silica having an average particle size D50 = 140 nm.
Inorganic fine particles D: Rutile-type titania obtained by the vapor phase method was treated with decylsilane in an aqueous system, and dried and pulverized to obtain hydrophobized titania having an average particle diameter D50 = 30 nm.
Inorganic fine particles E: Silica sol obtained by the sol-gel method was subjected to hexamethyldisilazane treatment, and dried and pulverized to obtain hydrophobized silica having an average particle diameter D50 = 250 nm.
・ Inorganic fine particle F: JR405 (manufactured by Rutile Titania Teica); average particle size = 210 nm

<Inorganic fine particle-dispersed polyester resin dispersion (1)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): Melting and mixing inorganic fine particles A: 2 parts by mass with a lab blast mill with respect to 98 parts by mass, an inorganic fine particle-dispersed polyester resin was obtained. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (1) was obtained. The composite resin fine particles had a volume average particle size of 0.15 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle-dispersed polyester resin dispersion (2)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): Melting and mixing 2 parts by mass of inorganic fine particles B with a lab blast mill with respect to 98 parts by mass, an inorganic fine particle-dispersed polyester resin was obtained. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (2) was obtained. The composite resin fine particles had a volume average particle size of 0.16 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (3)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): 96 parts by mass of inorganic fine particles A: 4 parts by mass was melt-mixed by a laboratory blast mill to obtain inorganic fine particle-dispersed polyester resin. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (3) was obtained. The composite resin fine particles had a volume average particle size of 0.17 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (4)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): Melting and mixing inorganic fine particles C: 2 parts by mass with a laboratory blast mill with respect to 98 parts by mass, an inorganic fine particle-dispersed polyester resin was obtained. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (4) was obtained. The composite resin fine particles had a volume average particle size of 0.16 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (5)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): 98 parts by mass of inorganic fine particles D: 2 parts by mass was melt-mixed by a laboratory blast mill to obtain inorganic fine particle-dispersed polyester resin. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (5) was obtained. The composite resin fine particles had a volume average particle size of 0.17 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (6)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): Melting and mixing 2 parts by mass of inorganic fine particles E with a lab blast mill with respect to 98 parts by mass, an inorganic fine particle-dispersed polyester resin was obtained. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (6) was obtained. The composite resin fine particles had a volume average particle size of 0.15 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (7)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): 2 parts by mass of inorganic fine particles F with respect to 98 parts by mass were melt-mixed by a laboratory blast mill to obtain inorganic fine particle-dispersed polyester resin. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (7) was obtained. The composite resin fine particles had a volume average particle size of 0.18 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Polyester resin dispersion (8)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent capable of dissolving the resin (1), and then the above resin is gradually added and stirred with a three-one motor to completely dissolve the oil. Got the phase. An appropriate amount of a dilute aqueous ammonia solution is added dropwise to the stirred oil phase, further added to ion-exchanged water for phase inversion emulsification, and solvent removal is performed while reducing the pressure with an evaporator, to obtain a polyester resin fine particle dispersion (8). Obtained. The composite resin fine particles had a volume average particle size of 0.19 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (9)>
Next, an amorphous polyester resin (1) was used to prepare a resin fine particle dispersion. Polyester resin (1): 92 parts by mass of inorganic fine particles A: 8 parts by mass was melt-mixed by a laboratory blast mill to obtain inorganic fine particle-dispersed polyester resin. A 5 L separable flask is charged with a considerable amount of ethyl acetate and isopropyl alcohol mixed solvent that can dissolve the resin, and then the above resin is gradually added, stirred with a three-one motor, and completely dissolved to obtain an oil phase. It was. A suitable amount of dilute aqueous ammonia solution is added dropwise to this stirred oil phase, and further added to ion-exchanged water for phase inversion emulsification. Further, solvent removal is performed while reducing the pressure with an evaporator, and polyester resin fine particles dispersed with inorganic fine particles dispersed therein. A liquid (9) was obtained. The composite resin fine particles had a volume average particle size of 0.20 μm. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

[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 diameter 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 diameter was 189 nm μm. . The solid content ratio of the yellow colorant dispersion was 21.5% 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 23.2% 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 350 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]
The melt viscosity at 120 ° C. of the release agent is as follows.
・ HNP9: 5mPa ・ s
・ PW500: 7 mPa · s
・ FT105: 11 mPa · s

<Releasing agent dispersion (1)>
HNP9 (Nippon Seiki): 400 parts by mass Fiber (polylactic acid nanofiber: diameter 100 nm): 8 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, dispersed with a pressure discharge type homogenizer at a pressure of 120 ° C. and 50 MPa, and further removed fibers accumulated in the supernatant to prepare a release agent dispersion (1). The solid content of the release agent dispersion (1) was 20%.

<Releasing agent dispersion (2)>
A release agent dispersion liquid (2) was prepared in the same manner as the preparation of the release agent dispersion liquid (1) except that the release agent of the release agent dispersion liquid (1) was changed to PW500 (Toyo Petrolite).

<Releasing agent dispersion (3)>
A release agent dispersion (3) was prepared in the same manner as the preparation of the release agent dispersion (1) except that the release agent of the release agent dispersion (1) was changed to FT105 (Nippon Seiki).

<Releasing agent dispersion (4)>
A release agent dispersion liquid (4) was prepared in the same manner as the preparation of the release agent dispersion liquid (1) except that the fibers of the release agent dispersion liquid (1) were replaced with carbon nanotubes (diameter 50 nm).

<Releasing agent dispersion (5)>
HNP9 (Nippon Seiki): 200 parts by mass Neogen SC (Daiichi Kogyo Seiyaku): 10 parts by mass Methyl ethyl ketone: 800 parts by mass Fiber (polylactic acid nanofiber: 100 nm in diameter): 4 parts by mass The above components were heated to 60 ° C. Dispersion was carried out for 20 minutes in an IKE Ultra Turrax T50, and then 800 parts by mass of ion exchange water was added to complete the dispersion. Next, the supernatant fiber was removed, and the methyl ethyl ketone portion was volatilized with light stirring for 24 hours. Thereafter, sieving was performed with a 75 μm sieving mesh to obtain a release agent dispersion (5). The solid content of the release agent dispersion 5 was 20%.

<Releasing agent dispersion (6)>
In the release agent dispersion liquid (1), a release agent dispersion liquid (6) was prepared in the same manner as the preparation of the release agent dispersion liquid (1) except that the fibers were excluded.

<Releasing agent dispersion (7)>
In the release agent dispersion (3), a release agent dispersion (7) was prepared in the same manner as the preparation of the release agent dispersion (3) except that the fibers were removed.

<Production of toner>
[Example 1]
Ion-exchanged water: 280 parts by weight Inorganic fine particle-dispersed polyester resin (1) Dispersion: 367 parts by weight Anionic surfactant: 2.8 parts by weight (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, 20% by weight)
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): 80 parts by weight was added and held for 5 minutes. The 1.0 wt% nitric acid aqueous solution was added as it was to adjust the pH to 3.0.

  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 a Coulter counter [TA-II] type (aperture) Diameter: 50 μm, manufactured by Coulter, Inc.) When the volume average particle diameter was 5.5 μm, 90 parts by mass of the amorphous polyester resin (1) dispersion and amorphous polyester resin (7 ) 90 parts by mass of the dispersion was added. After the addition for 30 minutes, the pH was adjusted to 9.0 using a 5 mass% aqueous sodium hydroxide solution. Thereafter, the temperature is raised to 90 ° C. and held at 90 ° C. for 3 hours, followed by cooling, filtration, and redispersion in ion-exchanged water until the electric conductivity of the filtrate is less than 20 μS / cm. After repeated washing, the toner was obtained by vacuum drying in an oven at 40 ° C. for 5 hours.

  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.

[Example 2]
Inorganic fine particle-dispersed polyester resin (1) Other than using the fine particle-dispersed polyester resin (2) dispersion instead of the dispersion, and using the release agent dispersion (2) instead of the release agent dispersion (1) Prepared toner (2) according to Example 1.

[Example 3]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (3) dispersion is used in place of the dispersion, and a release agent dispersion (3) is used in place of the release agent dispersion (1). Prepared toner (3) according to Example 1.

[Example 4]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (4) dispersion is used in place of the dispersion, and a release agent dispersion (4) is used in place of the release agent dispersion (1). Prepared toner (4) according to Example 1.

[Example 5]
Inorganic fine particle-dispersed polyester resin (1) Inorganic fine particle-dispersed polyester resin (5) is used in place of the dispersion, and release agent dispersion (5) is used in place of the release agent dispersion (1) Prepared toner (5) according to Example 1.

[Example 6]
According to Example 1 except that the inorganic fine particle dispersed polyester resin (4) dispersion was used in place of the inorganic fine particle dispersed polyester resin (1) dispersion and the black colorant dispersion was used in place of the cyan colorant dispersion. Thus, toner (6) was prepared.

[Example 7]
According to Example 1, except that the inorganic fine particle dispersed polyester resin (4) dispersion was used in place of the inorganic fine particle dispersed polyester resin (1) dispersion and the yellow colorant dispersion was used instead of the cyan colorant dispersion. Toner (7) was prepared.

[Example 8]
According to Example 1 except that the inorganic fine particle dispersed polyester resin (4) dispersion was used instead of the inorganic fine particle dispersed polyester resin (1) dispersion and the magenta colorant dispersion was used instead of the cyan colorant dispersion. Thus, toner (8) was prepared.

[Comparative Example 1]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (6) dispersion is used in place of the dispersion, and a release agent dispersion (6) is used in place of the release agent dispersion (1). Prepared toner (9) according to Example 1.

[Comparative Example 2]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (7) dispersion is used in place of the dispersion, and a release agent dispersion (6) is used in place of the release agent dispersion (1). Prepared toner (10) according to Example 1.

[Comparative Example 3]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (8) dispersion is used in place of the dispersion, and a release agent dispersion (7) is used in place of the release agent dispersion (1). Prepared toner (11) according to Example 1.

[Comparative Example 4]
Inorganic fine particle-dispersed polyester resin (1) A fine particle-dispersed polyester resin (9) dispersion is used in place of the dispersion, and a release agent dispersion (6) is used in place of the release agent dispersion (1). Prepared toner (12) according to Example 1.

<Inorganic fine particle-dispersed crystalline resin dispersion (10)>
[Resin dispersion (2)]
(Oil layer)
Styrene (manufactured by Wako Pure Chemical Industries, Ltd.): 30 parts by mass n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.): 10 parts by mass β-carboxyethyl acrylate (manufactured by Rhodia Nikka Co., Ltd.): 1.3 Parts by mass dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.): 0.4 parts by mass inorganic fine particles C: 2 parts by mass (water layer 1)
Ion-exchanged water: 17 parts by weight Anionic surfactant (Dowfax, manufactured by Dow Chemical): 0.4 parts by weight (water layer 2)
Ion-exchanged water: 40 parts by weight Anionic surfactant (Dowfax, manufactured by Dow Chemical): 0.05 part by weight Ammonium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.): 0.4 parts by weight The above oil layer components and water The components of layer 1 were placed in a flask and mixed with stirring to obtain a monomer emulsified dispersion. The components of the aqueous layer 2 were charged into the reaction vessel, the inside of the vessel was sufficiently replaced with nitrogen, and the reaction system was heated to 75 ° C. with an oil bath while stirring. The above monomer emulsified dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropping, the polymerization was further continued at 75 ° C., and the polymerization was terminated after 3 hours. As a result, an inorganic fine particle-dispersed polyester resin dispersion (10) was obtained. (The resin particle concentration was adjusted to 42% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (11)>
Ethylene glycol (Wako Pure Chemical Industries, Ltd.): 50 parts by mass Neopentyl glycol (Wako Pure Chemical Industries, Ltd.): 65 parts by mass Terephthalic acid (Wako Pure Chemical Industries, Ltd.): 96 parts by weight Inorganic Fine particle C: 2 parts by mass The above monomer was charged into a flask and heated to 190 ° C. over 1 hour. After confirming that the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. did. Further, while distilling off the generated water, the temperature was raised from the same temperature to 240 ° C. over 6 hours, and the dehydration condensation reaction was continued at 240 ° C. for further 4 hours to obtain a polyester resin.

Subsequently, this was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. A 0.37 wt% diluted ammonia water obtained by diluting reagent ammonia water with ion-exchanged water is placed in a separately prepared aqueous medium tank and heated at 120 ° C. with a heat exchanger at a rate of 0.1 liter per minute. Simultaneously with the polyester resin melt, it was transferred to the Cavitron. The Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² to obtain an inorganic fine particle-dispersed polyester resin dispersion (11). (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Inorganic fine particle dispersed polyester resin dispersion (12)>
Dodecanedioic acid (manufactured by Tokyo Chemical Industry Co., Ltd.): 92 parts by mass Octanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 58 parts by mass Inorganic fine particles C: 2 parts by mass After raising the temperature to 160 ° C. and confirming that the reaction system was uniformly stirred, 0.03 parts by mass of dibutyltin oxide was added. Further, while distilling off the water produced, the temperature was raised from the same temperature to 200 ° C. over 6 hours, and the dehydration condensation reaction was continued at 200 ° C. for another 4 hours to complete the reaction. After cooling the reaction liquid, solid-liquid separation was performed, and the solid material obtained was dried under vacuum at 40 ° C. to obtain a crystalline polyester resin. Next, 50 parts by mass of the crystalline polyester resin, 2 parts by mass of Neogen SC, and 200 parts by mass of ion-exchanged water are mixed, heated to 120 ° C., and dispersed with a pressure discharge type homogenizer, and the inorganic fine particle dispersed polyester resin A dispersion (12) was obtained. (The resin particle concentration was adjusted to 30% with ion-exchanged water)

<Production of toner>
[Example 9]
(Toner 13)
Inorganic fine particle-dispersed polyester resin dispersion (10): 150 parts by weight Cyan colorant dispersion: 30 parts by weight Release agent dispersion (1): 60 parts by weight Polyaluminum chloride: 0.4 parts by weight Ion exchange water: 100 parts by weight Part The above ingredients were thoroughly mixed and dispersed in a round stainless steel flask using IKE Ultra Turrax T50, and then heated to 46 ° C. while stirring the flask in a heating oil bath. After maintaining at 46 ° C. for 80 minutes, 70 parts by mass of the same inorganic fine particle-dispersed polyester resin dispersion (10) as above was gradually added thereto.

Then, after adjusting the pH in the system to 6.0 using a sodium hydroxide aqueous solution having a concentration of 0.5 mol / L, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while stirring was continued. Heat to 80 ° C. and hold for 5 hours. After completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed using 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times. When the pH of the filtrate was 6.54 and the electric conductivity was 6.5 μS / cm, No. 2 was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain a toner. Further, this toner was subjected to surface hydrophobization treatment with hexamethyldisilazane, silica (SiO ₂ ) fine particles having an average primary particle size of 40 nm, and an average primary particle size of 20 nm, which is a reaction product of metatitanic acid and isobutyltrimethoxysilane. Then, the metatitanic acid compound fine particles were added so that the coverage of each colored particle surface was 40%, and mixed with a Henschel mixer to prepare toner (13).

[Example 10]
Inorganic fine particle-dispersed polyester resin dispersion (11): 160 parts by weight Cyan colorant dispersion: 30 parts by weight Inorganic fine particle-dispersed polyester resin dispersion (12): 50 parts by weight Release agent dispersion (1): 60 parts by weight Poly Aluminum chloride: 0.4 parts by mass Ion-exchanged water: 100 parts by mass The above ingredients were thoroughly mixed and dispersed in a round stainless steel flask using IKE Ultra Turrax T50, and then heated in an oil bath for heating. Was heated to 48 ° C. with stirring. After maintaining at 48 ° C. for 60 minutes, 80 parts by mass of the same inorganic fine particle-dispersed polyester resin dispersion (11) as above was gradually added thereto.

  Then, after adjusting the pH in the system to 8.0 using an aqueous sodium hydroxide solution having a concentration of 0.5 mol / L, the stainless steel flask is sealed, and the stirring shaft seal is magnetically sealed while stirring is continued. Heat to 90 ° C. and hold for 3 hours. After completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times, and when the pH of the filtrate became 7.54 and the electric conductivity was 6.5 μS / cm, No. was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain a toner.

Further, this toner was subjected to surface hydrophobization treatment with hexamethyldisilazane, silica (SiO ₂ ) fine particles having an average primary particle size of 40 nm, and an average primary particle size of 20 nm, which is a reaction product of metatitanic acid and isobutyltrimethoxysilane. Then, the metatitanic acid compound fine particles were added so that the coverage of the surface of each colored particle was 40%, and mixed with a Henschel mixer to prepare toner (14).

[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.

[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 item]
With a developer, a photoreceptor and an image forming method for developing an electrostatic latent image, low temperature / low humidity (10 ° C., 20% RH) and high temperature / high humidity (by Fuji Xerox Co., Ltd.) shown in FIG. A print test of 5000 sheets (image area: 5%) was performed at 30 ° C. and 85% RH), and fine line reproducibility, image density unevenness, and haze degree were evaluated.

[Evaluation of fine line reproducibility]
The line breaks and line edge sharpness at the time of producing a 60 μm thin line image were determined by observing with a digital microscope VH-6200 (manufactured by Keyence Corporation). Specific evaluation criteria are as follows.
A: The fine line is uniformly filled with toner, and the edge portion is not disturbed.
○: The fine line is uniformly filled with the toner, but slight jaggedness is observed at the edge portion.
(Triangle | delta): Although a thin wire | line is filled up with toner substantially uniformly, a jaggedness is conspicuous in an edge part.

[Evaluation of image density]
After taking a predetermined number of copies of each developer under a predetermined environment, the developer is left overnight to copy an image having a 2 cm × 5 cm patch, and an image densitometer (X-Rite 404A) : Manufactured by X-Rite). The difference between the maximum value and the minimum value of the measured values is less than 0.5, ◯ is 0.5 or more and less than 0.8, and 0.8 or more is ×.

(Haze measurement method)
Haze (cloudiness) is represented by the ratio (Td / Tt) of diffuse light transmittance (Td) and total light transmittance (Tt), and based on the measurement method of JISK7136, a transparent sheet (Fuji Xerox Co., Ltd .: V507). ) The image formed above was prepared on a square test piece having a side of 50 mm, and measured using a single beam type haze computer (model HZ-1, manufactured by Suga Test Instruments Co., Ltd.). A smaller haze value is preferable, and 20% or more is unacceptable.

  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. 3 is a schematic diagram illustrating an example of a toner recycling unit in the image forming apparatus used in the present embodiment.

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)

A toner having a sea-island structure including a binder resin, a colorant, and a release agent, wherein the release resin is an island when the sea is the binder resin;
The release agent domain contains fibers,
The toner for developing an electrostatic charge image, wherein the binder resin contains 0.05 to 5 parts by mass of inorganic particles having a center particle size of 5 to 200 nm. The electrostatic image developing toner according to claim 1,
The fibers contained in the release agent exist randomly,
The toner for developing an electrostatic charge image, wherein the inorganic particles are hydrophobized silica. The electrostatic image developing toner according to claim 1 or 2,
A toner for developing an electrostatic charge image, wherein the release agent has a melt viscosity at 120 ° C. of 1 mPa · s to 10 mPa · s. The electrostatic charge image developing toner according to any one of claims 1 to 3,
The binder resin is an amorphous polyester resin,
Amorphous polyester resin derived from a polyester resin emulsion dispersion obtained by dissolving a polyester resin and inorganic particles in a mixture of a good solvent and a water-soluble poor solvent, neutralizing it with ammonia, and then dropping water to phase inversion emulsification. A toner for developing an electrostatic charge image. The electrostatic charge image developing toner according to any one of claims 1 to 3,
The toner for developing an electrostatic charge image, wherein the binder resin contains a crystalline resin.   An electrostatic charge image developing developer comprising the electrostatic charge developing toner according to any one of claims 1 to 5 and a carrier.   A latent image forming unit that forms a latent image on a latent image holding member, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and a transfer unit that transfers the developed image onto a transfer target. 6. A cartridge having the electrostatic charge developing composition according to claim 1, wherein the electrostatic charge developing developer includes the electrostatic charge developing toner according to claim 1. A resin particle dispersion in which amorphous polyester resin particles containing 0.05 to 5 parts by mass of inorganic particles having a center particle size of 5 to 200 nm are dispersed, and colorant particles in which colorant particles are dispersed Aggregation that forms agglomerated particles including the resin particles, the inorganic particles, the colorant particles, the release agent particles, and the fibers by mixing the dispersion and a release agent particle dispersion in which fibers and release agent particles are dispersed. Process,
Adjusting the pH in the flocculation system to stop flocculation growth;
And a step of heating the aggregated particles to a glass transition temperature or a melting point or higher of the resin fine particles, and fusing and coalescing to form toner particles. In the method for producing a toner for developing an electrostatic charge image according to claim 5,
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 dropping water to phase-invert and emulsify the amorphous polyester resin. A process for producing an electrostatic charge image developing toner, comprising using an emulsified dispersion. A latent image forming unit that forms a latent image on the latent image carrier, a developing unit that develops the latent image using a developer for developing an electrostatic charge, and the developed toner image via an intermediate transfer member or not. An image forming apparatus including: a transfer unit that transfers the toner image on the transfer member; and a fixing unit that adds and fixes the toner image on the transfer member.
The image forming apparatus according to claim 6, wherein the developer for developing an electrostatic charge is the developer for developing an electrostatic charge according to claim 6.

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