JP5637497B2 - Toner and toner production method - Google Patents

Description

The present invention relates to a toner used for image formation in an electrostatic copying process such as a copying machine, a facsimile machine, and a printer, a method for producing the toner, a developer using the toner, and an image forming method using the toner. .

Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The toner remaining on the photoconductor without being transferred to the recording medium is transferred to a recording medium such as paper and fixed to the recording medium such as paper. It is cleaned by a cleaning member such as a blade arranged in pressure contact therewith.
On the other hand, the toner is required to have excellent cleaning properties, good low-temperature fixing, and high image quality.

By the way, most of the binder resin occupying 70% or more of the constituent components of the toner is made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, large consumption of petroleum resources, and emission of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a so-called plant-derived resin is used as a binder resin, which is derived from a plant that takes in carbon dioxide in the atmosphere and grows, the resulting carbon dioxide only circulates in the environment, which causes a problem of global warming. There is a possibility that the problem of depletion of petroleum resources can be solved at the same time, and various toners using such plant-derived resins as binder resins have been proposed.

  Polylactic acid is a general-purpose and easy-to-obtain resin, but polylactic acid is a very hard resin, so that it is difficult to make a toner by a pulverization method, and it is crystalline only in L-form or D-form. Therefore, the solubility in organic solvents is extremely low, and it is difficult to make a toner by a polymerization method such as a dissolved resin suspension method.

Japanese Patent Application Laid-Open No. 2008-262179 of Patent Document 1 discloses that the solubility in an organic solvent can be improved by mixing the L-form and D-form of polylactic acid to reduce crystallinity. Even when a resin as a unit is used as a binder resin, a toner capable of achieving both high image density, toner fixability and storage stability, a developer using the toner, and image formation Although a method is disclosed, there is still room for improvement in terms of cleanability and high image quality due to uniform toner particles.

That is, since polylactic acid has a low molecular weight of the monomer unit and a large number of polar groups per molecular weight, a toner using polylactic acid with reduced crystallinity is greatly affected by humidity. For this reason, toner storage stability deteriorates, toner fluidity changes due to moisture absorption, and charge amount control is difficult.Especially, it is not affected by environmental changes from low temperature and low humidity to high temperature and high humidity. It is difficult to maintain and stabilize the image density.

In order to stabilize the charge amount, the particle size distribution of the toner particles is sharpened, but a classification step is necessary to remove fine powder and coarse powder, and toners that require a classification step are It is difficult to consume energy and contribute to global warming issues.

As described above, even if the toner contains polylactic acid having the possibility of simultaneously solving the problem of global warming and the depletion of petroleum resources, it has excellent low-temperature fixability and does not require a classification process. It is difficult to obtain a toner with a small particle size and a uniform particle size, and has a wide fixing width, excellent heat-resistant storage stability, and high stability of image density against changes in the use environment such as temperature and humidity. A toner containing polylactic acid having excellent cleaning properties and related technology have not been obtained yet, and further improvement and development are desired.

Toner using a plant-derived resin or a resin having polylactic acid as a constituent unit, having a small content of fine powder without being classified, having a sharp particle size distribution, having an irregular shape and excellent cleaning properties, and a method for producing the toner The purpose is to provide.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. By embedding and fixing the resin fine particles, the cleaning property of the toner containing the amorphous polyester resin containing the polyhydroxycarboxylic acid skeleton in the main chain is improved, and the fine powder content is small without passing through the classification step. It has been found that a toner having a uniform diameter can be obtained.
The embedded fixation is a phenomenon in which the resin fine particles are fixed by being partially submerged into the base particles while maintaining the particle shape on the surface of the toner base particles, and the shape of the resin fine particles is changed to change the toner base particles. It is different from the state of covering.

The present invention is solved by the following (1) to ( 12 ).
(1) A toner granulated in an aqueous medium containing at least a binder resin, a colorant and a release agent, wherein the binder resin contains a polyhydroxycarboxylic acid skeleton in the main chain. A crystalline polyester resin is included, and resin fine particles are embedded on the surface of the toner base particles within a range of a subsidence A / 5 to 2A / 3 (where A represents the diameter of the resin fine particles) and fixed. Toner.
(2) The toner according to (1), wherein the resin fine particles are polyester resin fine particles having a volume average particle diameter of 20 nm to 500 nm.
(3) The above described (1) and (2), wherein A>B> 0 is satisfied, where A is the diameter of the fine particles and B is the depth of penetration of the fine particles into the toner base. toner.
(4) The volume average particle diameter is 3 μm or more and 8 μm or less, the fine powder content is 15% or less with the number average particle diameter being 2.0 μm or less, and the volume average particle diameter (Dv) and the number average particle diameter ( The toner according to any one of (1) to (3), wherein a ratio (Dv / Dn) to Dn) is 1.15 or less.
(5) The binder resin has an amorphous polyhydroxycarboxylic acid skeleton, has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and has an optical purity X (%) represented by the following formula (1): The toner according to any one of (1) to (4) above, wherein the toner is a binder resin characterized by being 80% or less.
Optical purity X (%) = | X (L form) -X (D form) | ... Formula (1)
[However, X (L-form) represents the L-form ratio (mol%) contained in the non-crystalline polyester resin in terms of optically active monomer, and X (D-form) represents the non-formity in terms of optically active monomer. The D-form ratio (mol%) contained in crystalline polyester resin is represented. ]
(6) The toner according to any one of (1) to (5) above, wherein the amorphous polyhydroxycarboxylic acid skeleton is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms.
(7) The toner according to any one of (1) to (6), wherein the binder resin contains a linear polyester diol containing a polyhydroxycarboxylic acid skeleton.
( 8 ) A developer comprising the toner according to any one of (1) to ( 7 ) and a carrier.
(9) A developer container, wherein the developer according to ( 8 ) is contained.
( 10 ) An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image using a developer. An image forming apparatus having at least developing means for forming a visual image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium, An image forming apparatus, wherein the agent is the developer described in ( 8 ).
( 11 ) An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, and using the toner according to any one of (1) to ( 7 ) above for the electrostatic latent image. The image forming apparatus includes at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. Image forming method.
( 12 ) An electrostatic latent image carrier and at least developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image, A process cartridge that is detachable from a forming apparatus main body, wherein the developer is the developer described in ( 8 ).

  As will be understood from the following detailed and specific description, according to the present invention, not only a high-quality image with high reliability can be obtained in a toner comprising a plant-derived resin or a resin having polylactic acid as a structural unit. Since the content of fine powder is small and the particle size distribution is sharp, the classification process in the toner production process can be reduced. Furthermore, in the toner obtained according to the present invention, resin fine particles are fixed on the surface of the base particle, and the number of polar groups on the surface of the toner particle is reduced as the toner particle is deformed. To do. Further, the deformed shape can be controlled by the toner production conditions.

It is a schematic explanatory drawing which shows an example of the process cartridge used by this invention. It is a schematic explanatory drawing which shows an example of the image forming apparatus used for the image forming method of this invention. It is a schematic explanatory drawing which shows another example of the image forming apparatus used for the image forming method of this invention. 1 is a schematic explanatory diagram illustrating an example of a tandem color image forming apparatus used in an image forming method of the present invention. FIG. 5 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 4. 6 is a SEM photograph of toner in Example 5. It is a figure showing the sinking depth to the toner base particle of resin fine particles.

The material constituting the toner of the present invention will be described. Note that it is easy for a person skilled in the art to change or modify the present invention within the scope of the claims to form other embodiments, and these changes and modifications are included in the scope of the claims, The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

(toner)
The toner of the present invention is a toner that contains at least a binder resin, a colorant, a release agent, and resin fine particles, and is granulated in an aqueous medium, and includes a polyhydroxycarboxylic acid skeleton in the main chain. The resin particles are deformed due to the presence of resin fine particles on the surface of the base particles containing the reactive polyester resin, and the cleaning property of the toner is improved. In addition, it is hardly affected by humidity and has excellent environmental stability and high quality images.
It is not clear why the resin particles are less susceptible to humidity due to the presence of resin particles on the surface of the base particles, but the density of polar groups of the resin particles on the surface of the toner base particles is higher than the density of polar groups of the base particles. It is thought that this is because it is low.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together.
Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin because an aqueous dispersion of fine spherical resin particles is easily obtained. Polyester resin fine particles having an aromatic chain as the main chain and having a lower ester group concentration per molecular weight than the base particles are preferred because they are easily fixed to the amorphous polyester resin. Moreover, it is preferable to have a three-dimensional network structure.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles.
The method for preparing the aqueous dispersion of the resin fine particles is, for example, (i) in the case of the vinyl resin, selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material. (Ii) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (iii) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., precursor (monomer, oligomer, etc.) or solvent solution thereof (liquid) (It may be liquefied by heating.) A suitable emulsifier is dissolved in the solution, and then water is added to carry out phase inversion emulsification. (Iv) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) Resin prepared by any polymerization reaction mode such as addition, addition condensation, condensation polymerization, etc.) is pulverized using a mechanical pulverizer or jet pulverizer, and then classified to give resin fine particles. After being obtained, a method of dispersing in water in the presence of a suitable dispersant, (v) a polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) may be used in advance. A resin solution obtained by dissolving the resin prepared in (1) in a solvent in the form of a mist to obtain resin fine particles, and then dispersing the resin fine particles in water in the presence of an appropriate dispersant; (vi) polymerization reaction in advance (Addition polymerization, ring-opening polymerization, Add any poor solvent to a resin solution prepared by dissolving a resin prepared by addition, addition condensation, condensation polymerization, or the like in a solvent, or cool a resin solution previously dissolved in a solvent. And (vii) a polymerization reaction (addition polymerization, opening) in advance. (Vii) precipitating resin fine particles and then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. A resin solution prepared by dissolving a resin prepared by a ring polymerization, polyaddition, addition condensation, condensation polymerization, or the like in a solvent was dispersed in an aqueous medium in the presence of an appropriate dispersant. Then, the method of removing the solvent by heating or reduced pressure, etc., (viii) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) Melt resin A suitable preparation method includes a method in which an appropriate emulsifier is dissolved in a resin solution dissolved in an agent, and then water is added to perform phase inversion emulsification.

The resin fine particles preferably have a particle size of 20 nm to 500 nm. When the thickness is less than 20 nm, the effect of deforming is small and cleaning may be poor. When the thickness exceeds 500 nm, the toner base particles are not sufficiently fixed and fall off and are easily affected by humidity.

<Binder resin>
The binder resin of the toner of the present invention is characterized by containing an amorphous polyester resin (a) containing at least a polyhydroxycarboxylic acid skeleton in the main chain.
The non-crystalline polyester resin (a) mentioned here is specifically a resin containing a polycondensate such as lactic acid or hydroxyalkyl carboxylic acid as a repeating unit in its structure. These resins have a high concentration of ester groups in the resin backbone main chain, and a short alkyl chain in the side chain. Compared to conventional polyester resins with aliphatic / aromatic chains as the main chain, the concentration of ester groups per molecular weight is high, and in the non-crystalline state, it has high transparency and organic acids and hydroxyl groups represented by carboxylic acids. High affinity with various colorants can be obtained even though there are few functional groups such as.

  The polyhydroxycarboxylic acid skeleton has a (co) polymerized skeleton of hydroxycarboxylic acid, and can be formed by a method of directly dehydrating condensation of hydroxycarboxylic acid or a method of ring-opening polymerization of a corresponding cyclic ester. The polymerization method is preferably ring-opening polymerization of a cyclic ester from the viewpoint of increasing the molecular weight of the polyhydroxycarboxylic acid to be polymerized.

From the viewpoint of the transparency and thermal properties of the toner, the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid, more preferably a hydroxycarboxylic acid having 2 to 6 carbon atoms, such as lactic acid or glycolic acid. , 3-hydroxybutyric acid and the like are mentioned, and lactic acid is particularly preferred.
In addition to the hydroxycarboxylic acid, a cyclic ester of hydroxycarboxylic acid can be used as a raw material for the polymer. In this case, the hydroxycarboxylic acid skeleton of the resin obtained by polymerization is a hydroxycarboxylic acid constituting the cyclic ester. The acid is a polymerized skeleton.
For example, the polyhydroxycarboxylic acid skeleton of a resin obtained using lactide is a skeleton obtained by polymerizing lactic acid.

As the monomer for forming the polyhydroxycarboxylic acid skeleton of the amorphous polyester resin (a), those having optical isomers such as lactic acid and hydroxybutyric acid are preferable.
The non-crystalline polyester resin (a) contains a polyhydroxycarboxylic acid skeleton composed of these optically active monomers, and the polyhydroxycarboxylic acid composed of the optically active monomers has an optical purity X (%) = | X (L isomer) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio in terms of optically active monomer ( Mol%)] is preferably 80% or less. More preferably, it is 60% or less. Within this range, solvent solubility and resin transparency are improved.

  Taking lactic acid as an example, lactic acid monomers include L-form and D-form, and an amorphous polylactic acid skeleton is formed by setting the D-form ratio in the above range. Mixing other hydroxyalkyl carboxylic acids with the lactic acid monomer lowers the glass transition temperature of the resin, so other hydroxy acids, such as the monomers listed above, can coexist in order to impart the desired thermal properties to the resin. It is possible to obtain a resin.

It is also possible to copolymerize resins of other skeletons within the range where crystallinity and transparency are not impaired, for example, various diols, dicarboxylic acids, polyhydric alcohols such as glycerin and glycolic acid, malic acid, tartaric acid It is also possible to change the composition of the resin by using a polyhydric hydroxy acid together.
In order to obtain these resins, for example, a monomer such as lactic acid or other composition is mixed, and this is directly dehydrated and polymerized in the presence of an appropriate catalyst and alcohol if necessary. It may be prepared by any known method such as ring-opening polymerization via lactide, which is a dimer obtained by dehydration, and synthesis using an enzymatic reaction such as lipase.

  An amorphous resin can be obtained by using a suitable amount of L and D monomers as monomers to obtain a racemate. In the case of using lactide, L-lactide and D-lactide can be mixed and used, respectively, but ring-opening polymerization of meso-lactide or mixing of lactide of either D-form or L-form and meso-lactide A non-crystalline resin can be obtained also by using.

The weight average molecular weight (hereinafter abbreviated as Mw) of the non-crystalline polyester resin (a) is preferably from 7000 to 70,000, more preferably from 10,000 to 40, from the viewpoints of heat resistant storage stability and low temperature fixability. 15,000, most preferably 15,000-35,000.
The glass transition temperature of the non-crystalline polyester resin (a) is preferably 50 ° C. or higher and 70 ° C. or lower, and more preferably 55 ° C. or higher and 65 or lower. If the glass transition temperature is less than 50 ° C, the heat-resistant storage stability may be insufficient, and if it exceeds 70 ° C, the low-temperature fixability may be insufficient.

Here, the method for measuring the optical purity X is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polymer or toner having a polyester skeleton is treated with pure water, 1N sodium hydroxide and isopropyl alcohol. And then hydrolyzed by heating and stirring at 70 ° C. Subsequently, the solid content in the liquid is removed by filtration and neutralized by adding sulfuric acid to obtain an aqueous solution containing L- and / or D-lactic acid decomposed from the polyester resin. The aqueous solution was measured by a high performance liquid chromatograph (HPLC) using a chiral ligand exchange type column SUMICHILAR OA-5000 (manufactured by Sumika Chemical Analysis Co., Ltd.), and a peak area S (L ) And D-lactic acid-derived peak area S (D). The optical purity X can be determined from the peak area as follows.
X (L-form)% = 100 × S (L) / (S (L) + S (D))
X (D form)% = 100 × S (D) / (S (L) + S (D))
Optical purity X% = | X (L form) -X (D form) |

  When forming the polyhydroxycarboxylic acid skeleton, the diol (11) is added and copolymerized to obtain a polyester diol (a11) containing the polyhydroxycarboxylic acid skeleton. Preferred as diols are alkylene oxides of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (Alkylene oxide is hereinafter abbreviated as AO. Specific examples include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) These can be used in combination. More preferred are 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and AO adducts of bisphenol A, and particularly preferred is 1,3-propanediol.

  When the non-crystalline polyester resin (a) contains a linear polyester diol (a11) containing a polyhydroxycarboxylic acid skeleton, the low-temperature fixability is further improved, which is preferable. In addition, the amorphous polyester resin is obtained by reacting a linear polyester diol (a11) containing a polyhydroxycarboxylic acid skeleton with a polyester diol (a12) other than (a11) together with an extender. It is preferable to contain the chain polyester resin (A) because the heat resistant storage stability is further improved.

The polyester diol (a12) other than the linear polyester diol (a11) containing a polyhydroxycarboxylic acid skeleton is not particularly limited as long as it is a polyester diol other than the polyester diol (a11). For example, the same product as the reaction product of the diol (11) and the dicarboxylic acid (13) can be used. It is obtained by doing.
The polyester diol (a12) other than the polyester diol (a11) is preferably 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol). A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adduct (addition mole number 2-30) and one or more selected from these combinations, terephthalic acid, isophthalic acid, adipic acid , Succinic acid, and a reaction product with one or more selected from these combinations.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyester diol (a11) and the polyester diol (a12) other than the polyester diol (a11) is a viewpoint for adjusting the physical properties of the linear polyester resin (A). From 500 to 30,000 is preferable, more preferably from 1,000 to 20,000, and most preferably from 2,000 to 5,000.

As an extender used for elongation of the polyester diol (a11) and the polyester diol (a12) other than the polyester diol (a11), a polyester diol (a12) other than the polyester diol (a11) and the polyester diol (a11) may be used. Is not particularly limited as long as it has two functional groups capable of reacting with a hydroxyl group contained in the dicarboxylic acid (13) and its anhydride, polyisocyanate (15), and polyepoxide (19). Among them, bifunctional ones are mentioned.
Among these, from the viewpoint of compatibility between the polyester diol (a11) and the polyester diol (a12) other than the polyester diol (a11), preferred are a diisocyanate compound and a dicarboxylic acid compound, and more preferred is a diisocyanate. A compound.
Specifically, succinic acid, adipic acid, maleic acid (and anhydride), fumaric acid (and anhydride), phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4 '-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, etc., among which succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and anhydrous) Product), fumaric acid (and anhydride), and DI, is IPDI, most preferably maleic acid (and anhydride), fumaric acid (and anhydride), and IPDI.

The content of the extender in the linear polyester resin (A) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, from the viewpoints of transparency and thermal characteristics.
The mass ratio of the polyester diol (a11) containing the polyhydroxycarboxylic acid skeleton constituting the linear polyester resin (A) and the polyester diol (a12) other than the polyester diol (a11) is preferably 31:69. It is -90: 10, More preferably, it is 40: 60-80: 20 from a viewpoint of transparency and a thermal characteristic.

<Colorant>
The colorant used in the toner of the present invention is not particularly limited and can be appropriately selected from known colorants according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanentre 4R, Parared, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Rake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Rune, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc Green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green go , Acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and the like. These may be used individually by 1 type and may use 2 or more types together.
The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, The toner of each color can be obtained by appropriately selecting the type of the colorant, but is preferably a color toner.

Examples of the black material include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).
Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.
Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.
Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Examples of such resins include polyester, polylactic acid, styrene or its substituted polymer, styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, and polypropylene. , Epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin And paraffin wax. These may be used individually by 1 type and may use 2 or more types together. Among these, polyester and polylactic acid are preferable from the viewpoint of compatibility with the binder resin in the present invention.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste of a colorant containing water is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

<Other ingredients>
<Release agent>
The release agent used in the toner of the present invention is not particularly limited, and all known ones can be used, but in particular, a free fatty acid type carnauba wax, a polyethylene wax, a montan wax and an oxidized rice wax are used alone or in combination. Can be used. As the carnauba wax, those having fine crystallinity are preferable, those having an acid value of 5 mgKOH / g or less and a particle size of 1 μm or less when dispersed in the toner binder are preferable. The montan wax generally refers to a montan wax refined from a mineral, and like a carnauba wax, it is preferably a microcrystal and an acid value of 5 to 14 mgKOH / g. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30. The reason is that these waxes are finely dispersed in the toner binder resin of the present invention, so that it is easy to obtain a toner excellent in offset prevention, transferability and durability as described later. These waxes can be used alone or in combination of two or more.

As other mold release agents, any conventionally known mold release agents such as solid silicone wax, higher fatty acid higher alcohol, montan ester wax, polyethylene wax and polypropylene wax can be mixed and used.
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-120 degreeC is preferable and 70-90 degreeC is more preferable. If the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 120 ° C., cold offset may easily occur during fixing at a low temperature.

  The melting point of the release agent is, for example, a sample that is heated up to 200 ° C. using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), and cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. And the maximum peak temperature of the heat of fusion can be determined as the melting point.

  The melt viscosity of the release agent is preferably 5 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the release agent. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  The content of the release agent in the toner is preferably 1 to 20% by mass and more preferably 3 to 10% by mass with respect to the toner resin component. If it is less than 1% by mass, the effect of preventing offset is insufficient, and if it exceeds 20% by mass, transferability and durability are deteriorated.

  The method of introducing the release agent includes a method of kneading and dispersing inside the resin, a method of introducing by dispersing or dissolving in a solvent or a monomer droplet in a chemical toner such as a dissolution suspension method or an emulsion polymerization method, a method of dispersing in water Any method such as a method of incorporating the released release agent into the particles by agglomeration and coalescence or a method of chemically adding to the particle surface is possible.

<Charge control agent>
In addition, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, a triphenylmethane dye, a molybdate chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (all manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (Nippon Carlit Co., Ltd.); quinacridone, azo pigment; sulfonic acid And a polymer compound having a functional group such as a group, a carboxyl group, and a quaternary ammonium salt.

  The charge control agent may be melted and kneaded together with a master batch in which a colorant and a resin are combined, and then dissolved or dispersed, and when dissolved or dispersed directly in the organic solvent together with the toner components. It may be added, or may be fixed on the toner surface after the production of the toner particles. Among these, a method of imparting a fluorine-containing quaternary ammonium salt to the particle surface is preferably used as the charge control agent.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount exceeds 5% by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the developer fluidity is reduced, and the image The density may be lowered, and if it is less than 0.01% by mass, the charge start-up property and the charge amount are not sufficient, and the toner image may be easily affected.

<Shaping agent>
Further, for the purpose of making the shape of the toner base particles themselves atypical, it is possible to add a modifying agent to the toner as necessary.
Although there is no restriction | limiting in particular as said atypifying agent, It is preferable to contain the layered inorganic mineral which modified | denatured at least one part of the ion of the layer which a layered inorganic mineral has with organic substance ion. As the modified layered inorganic mineral, one having a smectite basic crystal structure modified with an organic cation is desirable. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.
Examples of the organic cation modifying agent of the modified layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts, and quaternary alkyl ammonium salts are preferable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
As the organic anion modifier, branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least a part of the layered inorganic mineral with organic ions, the oily phase having appropriate hydrophobicity and the toner phase containing the toner composition has non-Nutnian viscosity, and the toner can be atypified. At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.

The modified layered inorganic mineral can be selected as appropriate, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.
Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
R ₁ (OR ₂ ) nOSO ₃ M General formula (1)
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

<External additive>
Various external additives can be added to the toner for purposes such as fluidity modification, charge amount adjustment, and electrical property adjustment. The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, stearin) Metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Also manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.
Hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination, but the average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, and more preferably 5 to 70 nm. More preferably, the primary particles subjected to the hydrophobization treatment include at least two types of inorganic fine particles having an average particle diameter of 20 nm or less and at least one type of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by the BET method of the said inorganic fine particle is 20-500 m < ² > / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

<Fluidity improver>
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a fluoride. Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

<Cleaning improver>
A cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

<Magnetic material>
There is no restriction | limiting in particular as a magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

Hereinafter, a method for producing a toner in the present invention will be described.
Here, although a preferable manufacturing method is shown, it is not limited to this.
The toner production method of the present invention is by granulating a toner after preparing an emulsion or dispersion by emulsifying or dispersing a solution or dispersion of a toner material in an aqueous medium. ) To (7).

(1) Toner Material Dissolution or Preparation of Dispersion Liquid The toner material dissolution or dispersion liquid is obtained by dissolving or dispersing the toner material in an organic solvent.
The toner material is not particularly limited as long as toner can be formed, and can be appropriately selected according to the purpose.
For example, the binder resin, if necessary, a second binder resin different from the binder resin, an active hydrogen group-containing compound if necessary, and a modified polyester capable of reacting with the active hydrogen group-containing compound ( At least a prepolymer) and, if necessary, other components such as a release agent, a colorant, and a charge control agent.
A solution or dispersion of the toner material can be obtained by dissolving or dispersing the toner material in the organic solvent.
The organic solvent is removed during or after the toner granulation.
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, methyl isobutyl ketone, and the like, and ester solvents are preferable, and ethyl acetate is particularly preferable.
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 60 mass parts- 140 mass parts is more preferable, and 80 mass parts-120 mass parts is still more preferable.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later. Alternatively, when the solution or dispersion of the toner material is added to the aqueous medium, it may be added to the aqueous medium together with the solution or dispersion.

(2) Preparation of aqueous medium The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Of these, water is particularly preferable.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like.
Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

In addition, in the aqueous medium, if necessary, from the viewpoint of stabilizing the oil droplets of the dissolved or dispersed liquid during emulsification or dispersion described later, and obtaining a desired shape while sharpening the particle size distribution. It is preferable to use an agent.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, anionic surfactants having a fluoroalkyl group, and those having a fluoroalkyl group are suitable. It is mentioned in.
Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydro Xylethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like.
Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); , F150 (manufactured by Neos) and the like.
Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type cationic surfactants, and cationic surfactants having a fluoroalkyl group.
Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like.
Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. .
Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, and the like. Aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Examples of commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Ftergent F-300 (manufactured by Neos).
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.
Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.
Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide and the like.
Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.
Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.
Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.
Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.
Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.

In the case where a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as a binder resin for the dissolution or dispersion, the aqueous medium includes, for example, dibutyltin laurate and dioctyltin laurate. A catalyst in the reaction can also be used.

(3) Emulsification or dispersion The dissolution or dispersion of the toner material in the aqueous medium is preferably performed by dispersing the dissolution or dispersion of the toner material in the aqueous medium while stirring.
The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Aihara Seisakusho), TK Fillmix, TK Pipeline Homomixer (made by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (Mitsui Miike Chemical Industries) Co., Ltd.), Capitoron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) and other continuous emulsifiers, Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer (Nanomizer Co., Ltd.), APV Gaulin High-pressure emulsifiers (made by Gaulin), membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), Bro mixer (Hiyaka Kogyo Co., Ltd.) vibration type emulsifying machine such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.) and the like.
Among these, it is preferable to use APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer from the viewpoint of uniform particle size.
In the case where a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as the first binder resin in the solution or dispersion, the reaction proceeds during the emulsification or dispersion.

The reaction conditions are not particularly limited and can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is 10 minutes to 40 hours is preferable, and 2 hours to 24 hours is more preferable.

(4) Addition of resin fine particles By gradually adding a dispersion of resin fine particles containing resin fine particles to the aqueous medium after the emulsification or dispersion step, the fine powder and resin fine particles generated by the emulsification do not remain in the aqueous medium, In addition, the particle diameter can be uniformly converged. At this time, the time for converging is preferably within 5 minutes to 120 minutes.
If the time for converging is less than 5 minutes, the resin fine particles cannot be sufficiently fixed, and if longer than 120 minutes, they are completely buried in the toner base particles.
The submerged depth (B) of the fine particles into the toner base is preferably A / 12 or more and less than A / 1.2, where A is the diameter of the fine particles, and A / 3 or more and 2A / 5. More preferably, it is as follows .
The sinking depth (B) can be adjusted by the monomer component, the particle size of the resin fine particles, the convergence time, and the like.
The acid value of the resin is preferably from 6 mgKOH / g to 45 mgKOH / g, and more preferably from 12 mgKOH / g to 45 mgKOH / g.
The particle size of the resin fine particles is preferably 15 nm to 530 nm, and more preferably 100 to 500 nm.

Since the resin fine particles have a lower affinity with the aqueous medium than the toner base particles, if the resin fine particles are dispersed in the aqueous medium in advance, the resin fine particles are included in the toner base particles in the emulsification or dispersion process, and the toner particles are deformed. I can't.
The addition amount of the resin fine particles is preferably 0.25 parts by weight or more and less than 10 parts by weight with respect to 100 parts of the toner base particles. If the amount is less than 0.25 parts by weight, the exposed part of the toner base particles is much susceptible to the influence of humidity, and if it is more than 10 parts by weight, the effect of deforming is reduced.

(5) Removal of solvent The organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

(6) When the organic solvent is removed, such as washing and drying classification, toner particles are formed.
The toner particles can be washed, dried, etc., and then classified as desired.
The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.
When a dispersion stabilizer that is soluble in an acid / alkali such as calcium phosphate is used as the dispersion medium, toner particles are dissolved by a method such as dissolving the dispersion stabilizer with an acid such as hydrochloric acid and washing with water. Can be removed.

(7) External addition of a charge control agent / release agent, etc. The toner particles thus obtained are, if necessary, particles of a release agent, charge control agent, etc., which are inorganic fine particles such as silica fine particles and titanium oxide fine particles. Further, by mixing them together or applying a mechanical impact force, it is possible to prevent the particles such as the release agent from detaching from the surface of the toner particles.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture by a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board, etc. are mentioned.
As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery). Manufactured by Seisakusho), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

The toner of the present invention is not particularly limited with respect to various physical properties such as shape and size, and can be appropriately selected according to the purpose. However, the following volume average particle diameter (Dv), volume average It is preferable to have particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, offset non-occurrence temperature, and the like.

The volume average particle diameter (Dv) of the toner is preferably 3 μm to 8 μm, for example.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is more preferably 1.00 to 1.25.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, with the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may occur easily, and if it exceeds 1.30, it will be difficult to obtain a high-resolution and high-quality image, and toner particles in the developer balance will be generated. Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.25, the storage stability, the low-temperature fixability, and the hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent.

With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 mm to 30 mm.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours.
The penetration can be measured by cooling the toner to room temperature and performing a penetration test.
In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The minimum fixing temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The roll temperature is the lower limit fixing temperature.

The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each color of solid images of red, blue, and green as single colors of yellow, magenta, cyan, and black, and solid colors of each color. It can be determined by adjusting so that it is developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

The acid value of the toner is preferably, for example, 1.0 to 50.0 (KOH mg / g), and more preferably 3 to 35 (KOH mg / g). By giving the toner an acid value, it becomes easy to be negatively charged.

<Developer>
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately.
The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time.

Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium ( Mn—Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 emu / g to 120 emu / g) are preferable in terms of securing image density.
Further, a weakly magnetized material such as a copper-zinc (Cu—Zn) type (30 emu to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred.
These may be used alone or in combination of two or more.
The core material has a volume average particle size of preferably 10 μm to 150 μm, more preferably 20 μm to 80 μm.
When the average particle diameter (volume average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color with many solid portions, the reproduction of the solid portions may be particularly poor.

The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin.
These may be used individually by 1 type and may use 2 or more types together.
Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin.
Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin.
Examples of the halogenated olefin resin include polyvinyl chloride.
Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.
The resin layer may contain conductive powder or the like, if necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide.
The average particle diameter of these conductive powders is preferably 1 μm or less.
When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing.

Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90% by mass to 98% % By mass is preferable, and 93% by mass to 97% by mass is more preferable.

<Toner container>
The toner-containing container of the present invention is formed by filling the container of the toner of the present invention or the developer. There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably. The size, shape, structure, material, etc. of the container body containing toner is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. The spiral surface irregularities are formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

<Process cartridge>
The process cartridge used in the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image, and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to develop a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and conveys the developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on an image forming apparatus used in the present invention described later.
Here, for example, as shown in FIG. 1, the process cartridge contains an electrostatic latent image carrier (101), and charging means (102), developing means (104), transfer means (108), cleaning means. (107) and other means as required.
In FIG. 1, (103) indicates exposure by an exposure means, and (105) indicates a recording medium.
Next, the image forming process by the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier (101) is charged by the charging means (102) and rotated by the exposure means (not shown) while rotating in the arrow direction. By exposure (103), an electrostatic latent image corresponding to the exposure image is formed on the surface.
The electrostatic latent image is developed by the developing means (104), and the obtained visible image is transferred to the recording medium (105) by the transfer means (108) and printed out.
Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by a cleaning unit (107), further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

<Image Forming Method and Image Forming Apparatus>
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.
The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. The other means, for example, a static elimination means, a cleaning means, a recycling means, a control means, etc. are provided.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is not particularly limited in terms of material, shape, structure, size, and the like. However, the shape is preferably a drum shape, and the material is an inorganic photosensitive material such as amorphous silicon or selenium, or an organic photosensitive material such as polysilane or phthalopolymethine. Body (OPC), and the like.
Among these, amorphous silicon is preferable from the viewpoint of long life.
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do.

The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. .
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
Further, the charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner.

Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Suitable examples include a developer that contains at least a developer and that can be applied to the electrostatic latent image in a contact or non-contact manner.
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. Well, for example, a developer having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller is preferable.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. .
Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force.
As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit.
The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel.
There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable.

Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG.
An image forming apparatus (100) shown in FIG. 2 includes a photosensitive drum (10 (hereinafter referred to as “photosensitive member 10”)) as the electrostatic latent image carrier, a charging roller (20) as the charging unit, An exposure device (30) as the exposure means, a development device (40) as the development means, an intermediate transfer member (50), a cleaning device (60) as the cleaning means having a cleaning blade, and the charge eliminating device A neutralizing lamp (70) as a means.
The intermediate transfer member (50) is an endless belt, and is designed to be movable in the direction of the arrow in the figure by three rollers (51) that are arranged inside and stretched.
A part of the three rollers (51) also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member (50).
An intermediate transfer body cleaning blade (90) is disposed in the vicinity of the intermediate transfer body (50), and a visible image (toner image) is transferred (secondary transfer) to the recording medium (95). A transfer roller (80) serving as the transfer means to which a transfer bias for applying the transfer bias can be applied.
Around the intermediate transfer member (50), there is a corona charger (58) for applying a charge to the visible image on the intermediate transfer member (50) in the rotational direction of the intermediate transfer member (50). It is arranged between the contact portion between the electrostatic latent image carrier (10) and the intermediate transfer member (50) and the contact portion between the intermediate transfer member (50) and the recording medium (95).
The developing device (40) includes a developing belt (41) as a developer carrier, and a black developing unit (45K), a yellow developing unit (45Y), and a magenta developing unit (45M) provided around the developing belt (41). ) And a cyan developing unit (45C).
The black developing unit (45K) includes a developer container (42K), a developer supply roller (43K), and a developing roller (44K).
The yellow developing unit (45Y) includes a developer container (42Y), a developer supply roller (43Y), and a developing roller (44Y).
The magenta developing unit (45M) includes a developer container (42M), a developer supply roller (43M), and a developing roller (44M).
The cyan developing unit (45C) includes a developer container (42C), a developer supply roller (43C), and a developing roller (44C).
The developing belt (41) is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier (10).

In the image forming apparatus (100) shown in FIG. 2, for example, the charging roller (20) uniformly charges the photosensitive drum (10).
An exposure device (30) performs imagewise exposure on the photosensitive drum (10) to form an electrostatic latent image.
The electrostatic latent image formed on the photosensitive drum (10) is developed by supplying toner from the developing device (40) to form a visible image (toner image).
The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member (50) by the voltage applied from the roller (51), and further transferred onto the transfer paper (95) (secondary transfer). The
As a result, a transfer image is formed on the transfer paper (95).
The residual toner on the photoconductor (10) is removed by the cleaning device (60), and the charge on the photoconductor (10) is once removed by the charge eliminating lamp (70).

Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG.
The image forming apparatus (100) shown in FIG. 3 does not include the developing belt (41) in the image forming apparatus (100) shown in FIG. 2, and a black developing unit (45K), Except that the yellow developing unit (45Y), the magenta developing unit (45M), and the cyan developing unit (45C) are directly opposed to each other, the image forming apparatus (100) shown in FIG. 2 has the same configuration. The same effect is exhibited.
In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG.
The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus.
The tandem image forming apparatus includes a copying machine main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (ADF) (400).
The copying machine main body (150) is provided with an endless belt-like intermediate transfer member (50) at the center.
The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16), and can rotate clockwise in FIG.
An intermediate transfer body cleaning device (17) for removing residual toner on the intermediate transfer body (50) is disposed in the vicinity of the support roller (15).
The intermediate transfer member (50) stretched between the support roller (14) and the support roller (15) has four image forming units (18) of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing device (120) arranged opposite to each other is arranged.
An exposure device (21) is disposed in the vicinity of the tandem developing device (120).
A secondary transfer device (22) is disposed on the side of the intermediate transfer member (50) opposite to the side on which the tandem developing device (120) is disposed.
In the secondary transfer device (22), a secondary transfer belt (24), which is an endless belt, is stretched between a pair of rollers (23), and a recording medium (transfer paper) conveyed on the secondary transfer belt 24 is transferred. ) And the intermediate transfer member (50) can contact each other.
A fixing device (25) is disposed in the vicinity of the secondary transfer device (22).
The fixing device (25) includes a fixing belt (26) that is an endless belt, and a pressure roller (27) that is pressed against the fixing belt (26).
In the tandem image forming apparatus, in the vicinity of the secondary transfer device (22) and the fixing device (25), a sheet reversing device (28) for reversing the transfer paper for image formation on both sides of the transfer paper. ) Is arranged.

Next, full color image formation (color copying) using the tandem developing device (120) will be described.
That is, first, a document is set on the document table (130) of the automatic document feeder (ADF) (400) or the automatic document feeder (400) is opened and the contact glass (32) of the scanner (300) is opened. A document is set on the document and the automatic document feeder (400) is closed.
When a start switch (not shown) is pressed, when a document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32). ) Immediately after the document is set on the scanner (300), the first traveling body (33) and the second traveling body (34) travel.
At this time, light from the light source is irradiated by the first traveling body (33) and reflected light from the document surface is reflected by the mirror in the second traveling body (34), and is read through the imaging lens (35). The color original (color image) is read at (36), and is read as black, yellow, magenta and cyan image information.
Each image information of black, yellow, magenta, and cyan is stored in each image forming unit (18) (black image forming unit, yellow image forming unit, magenta image forming unit, And cyan image forming means), and each image forming means forms toner images of black, yellow, magenta, and cyan.

That is, each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device (120) is as shown in FIG. Electrostatic latent image carrier (10) (black electrostatic latent image carrier (10K), yellow electrostatic latent image carrier (10Y), magenta electrostatic latent image carrier (10M), and An electrostatic latent image carrier for cyan (10C), a charging device (160) for uniformly charging the electrostatic latent image carrier (10), and an image corresponding to each color image based on each color image information An exposure apparatus that exposes the electrostatic latent image carrier (L in FIG. 5) and forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image Each color toner (black toner, yellow toner, magenta toner And a cyan toner), a developing device 61 for forming a toner image with each color toner, a transfer charger (62) for transferring the toner image onto the intermediate transfer member (50), and a cleaning device (63) and a static eliminator (64), and each monochrome image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color.

The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred onto the intermediate transfer member (50) that is rotationally moved by the support rollers (14), (15), and (16). A black image formed on the electrostatic latent image carrier (10K), a yellow image formed on the yellow electrostatic latent image carrier (10Y), and a magenta electrostatic latent image carrier (10M). The formed magenta image and the cyan image formed on the cyan electrostatic latent image carrier (10C) are sequentially transferred (primary transfer).
Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member (50) to form a composite color image (color transfer image).
On the other hand, in the paper feed table (200), one of the paper feed rollers (142) is selectively rotated so that the sheet (recording paper) is fed from one of the paper feed cassettes (144) provided in the paper bank (143). ), Separated one by one by the separation roller (145), sent to the paper feed path (146), and conveyed by the conveyance roller (147) to the paper feed path (148) in the copier body (150). Guide and stop against the registration roller (49).
Alternatively, the sheet feed roller (142) is rotated to feed out the sheets (recording paper) on the manual feed tray (54), separated one by one by the separation roller (145), and put into the manual feed path (53). Stop against the registration roller (49).
The registration roller (49) is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

Then, the registration roller (49) is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member (50), and the intermediate transfer member (50), the secondary transfer device (22), The sheet (recording paper) is fed between the sheets, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device (22). A color image is transferred and formed on (recording paper).
The residual toner on the intermediate transfer member (50) after the image transfer is cleaned by the intermediate transfer member cleaning device (17).
The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device (22) and sent to the fixing device (25). In the fixing device (25), heat and pressure are applied. The composite color image (color transfer image) is fixed on the sheet (recording paper).
Thereafter, the sheet (recording paper) is switched by the switching claw (55) and discharged by the discharge roller (56) and stacked on the discharge tray (57), or switched by the switching claw (55) and the sheet is reversed. The image is reversed by the device (28) and guided again to the transfer position, and an image is recorded also on the back surface. Then, the image is discharged by the discharge roller (56) and stacked on the discharge tray (57).

  Examples of the present invention will be described below, but the present invention is not limited to the examples.

<Manufacture of polyester resin fine particles>
[Production Example 1]
A mixture comprising 1,578 parts of terephthalic acid, 83 parts of isophthalic acid, 374 parts of ethylene glycol and 730 parts of neopentyl glycol was heated in an autoclave at 260 ° C. for 2.5 hours to carry out an esterification reaction. Next, 0.262 parts of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under this condition, the polycondensation reaction is continued, and after 1.5 hours, the system is brought to atmospheric pressure with nitrogen gas. The mixture was stirred at 255 ° C. for 30 minutes and discharged into a sheet. And after fully cooling to room temperature, this was grind | pulverized with the crusher and the polyester resin microparticles | fine-particles a-1 were obtained using the sieve of 1-6 mm of openings. Table 1 shows the monomer component, acid value, and weight average molecular weight of resin 1 of the fine particles.

[Production Examples 2 to 18]
21 types of polyester resin fine particles a-2 to a-22 were obtained in the same manner as in [Polyester resin fine particles a-1] except that the monomers shown in Table 1 were used. It means resin fine particles a-1 ").

モノマーの単位はすべてモルである。

All monomer units are moles.

[Production Example 19] (Production of fine particle dispersion (w-1))
In a 2 L glass container with a jacket, 200 parts of [resin fine particles a-1], 35 parts of ethylene glycol mono-n-butyl ether, and 0.5% by weight aqueous solution of polyvinyl alcohol (Unitika Ltd. “Unitika Poval” 050G) 35 parts of PVA-1) and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 equivalents of the total amount of carboxyl groups contained in the polyester resin [1] were added, and this was opened. When stirring at 6,000 rpm using a desktop homodisper (manufactured by Special Machine Industries Co., Ltd., TK Robotics), no precipitation of resin particles was observed at the bottom of the container, and it was in a completely floating state. It was confirmed that Therefore, this state was maintained, and hot water was passed through the jacket after 10 minutes for heating. When the temperature in the container reached 68 ° C., the stirring was set at 7,000 rpm, the temperature in the container was kept at 68 to 70 ° C., and the mixture was further stirred for 20 minutes to obtain a milky white uniform aqueous dispersion. Then, cold water was poured into the jacket, cooled to room temperature while stirring at 3500 rpm, and filtered using a stainless steel filter (635 mesh, plain weave). As a result, almost no resin particles remained on the filter. The analysis results of the obtained filtrate (fine particle dispersion w-1) are shown in Table 2.

[Production Examples 20 to 36] (Production of fine particle dispersions (w-2 to w-22))
In the same manner as in Production Example 19, fine particle dispersions were produced at the ratios shown in Table 2 to obtain (fine particle dispersions w-2 to 22).

<Production of Amorphous Polyester Resin (a)>
-L-lactide 70 parts by mass-D-lactide 30 parts by mass-ε-caprolactone 5 parts by mass-stannous octoate 0.03 parts by mass In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube The above raw materials were added and ring-opening polymerization was performed at 190 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, residual lactide was distilled off under reduced pressure to obtain [amorphous polyester resin (a)] containing a polyhydroxycarboxylic acid skeleton.
[Non-crystalline polyester resin (a)] had a number average molecular weight of 9,200, a weight average molecular weight of 37,000, and an optical purity of 40%.

<Preparation of master batch (MB)>
1200 parts by mass of water, 540 parts by mass of carbon black (“PB-k7: Printex 60”, manufactured by Degussa, DBP oil absorption = 114 ml / 100 g, pH = 7), and 1200 parts by mass of the resin (a) were mixed with a Henschel mixer ( (Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

<Synthesis of ketimine>
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 418.

<Preparation of oil phase>
In a beaker, 50 parts by mass of the [amorphous polyester resin (a)] and 130 parts by mass of ethyl acetate were added, stirred and dissolved to obtain a resin solution.
Next, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5 mg KOH / g, penetration = 1.5 mm (40 ° C.)) and 10 parts by mass of the master batch were charged, and a bead mill (“ Ultraviscomill "(manufactured by Imex) is used to prepare a raw material solution by three passes under conditions where the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and 80% by volume of 0.5 mm zirconia beads are filled. Then, 2.7 parts by mass of the ketimine was added and dissolved to prepare a toner material solution or dispersion.

<Preparation of aqueous phase>
3700 parts by weight of water, 560 parts by weight of ethyl acetate, 370 parts by weight of a 50.0% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate ("Eleminol MON-7", manufactured by Sanyo Chemical Industries Ltd.), 1 part by weight of magnesium chloride, U- 5 parts by mass of CAT was mixed and stirred to obtain a mixed solution (aqueous phase).

<Emulsification or dispersion>
150 parts by mass of the aqueous phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 100 parts by mass of the toner material dissolved or dispersed is added. The mixture was added and mixed for 10 minutes to prepare an emulsified dispersion (emulsified slurry).

<Addition and convergence of resin fine particles>
30 wt% fine particle dispersion w-1 having an average volume particle diameter of 25 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. At this time, the time required for addition was 60 minutes.

<Removal of organic solvent>
The emulsified slurry after convergence was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 1 hour, aging was performed at 60 ° C. for 5 hours to obtain a dispersed slurry.

<Washing and drying>
After filtering 100 parts by mass of the dispersion slurry under reduced pressure, adding 300 parts by mass of ion exchange water to the filter cake, mixing with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtering three times. And a final filter cake was obtained.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner base particles of Example 1.

<External additive treatment>
To 100 parts by mass of the obtained toner base particles, 1.0 part by mass of hydrophobic silica (“H2000”, manufactured by Clariant Japan Co.) as an external additive was added to a peripheral speed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was mixed at 30 m / s for 30 seconds and rested for 1 minute for 5 cycles, and sieved with an opening of 35 μm mesh to produce a toner.

<Creation of carrier>
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (manufactured by Toray Dow Corning Silicone, SR2411), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added, A coating layer forming solution was prepared by dispersing with a homomixer for 20 minutes.
The coating layer forming liquid was coated on the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to produce a magnetic carrier.

<Production of developer>
A two-component developer was manufactured by ball mill mixing 5 parts by mass of each toner treated with an external additive and 95 parts by mass of the carrier.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-2 having an average volume particle diameter of 50 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 2 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-3 having an average volume particle diameter of 80 nm was added in an amount of 0.01 part by weight after completion of the emulsification or dispersion process. 3 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-4 having an average volume particle diameter of 110 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 4 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-5 having an average volume particle size of 230 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. A toner of 5 was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-6 having an average volume particle diameter of 300 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 6 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-7 having an average volume particle size of 120 nm was added in an amount of 0.01 part by weight after completion of the emulsification or dispersion process. 7 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-8 having an average volume particle diameter of 190 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 8 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-9 having an average volume particle diameter of 450 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 9 toner was obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-10 having an average volume particle size of 490 nm was added in an amount of 0.01 part by weight after completion of the emulsification or dispersion process. Ten toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-11 having an average volume particle diameter of 400 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 11 toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-12 having an average volume particle size of 350 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 12 toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-13 having an average volume particle size of 150 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 13 toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-14 having an average volume particle size of 210 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 14 toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-15 having an average volume particle size of 15 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 15 toners were obtained.

Example 30 was conducted in the same manner as in Example 1 except that about 30 wt% fine particle dispersion w-16 having an average volume particle diameter of 530 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 16 toners were obtained.

[Comparative Example 1]
Comparative Example as in Example 1, except that about 30 wt% fine particle dispersion w-17 having an average volume particle size of 12 nm is added in an amount of 0.01 part by weight after the emulsification or dispersion process. 1 toner was obtained.

[Comparative Example 2]
Comparative Example as in Example 1 except that about 30 wt% fine particle dispersion w-18 having an average volume particle size of 15 nm is added in 0.01 parts by weight after the emulsification or dispersion process. 2 toner was obtained.

[Comparative Example 3]
Comparative Example as in Example 1, except that about 30 wt% fine particle dispersion w-19 having an average volume particle size of 510 nm is added in an amount of 0.01 part by weight after the emulsification or dispersion process. 3 toner was obtained.

[Comparative Example 4]
Comparative Example as in Example 1 except that about 30 wt% fine particle dispersion w-20 having an average volume particle diameter of 550 nm was added in an amount of 0.01 part by weight after the emulsification or dispersion process. 4 toner was obtained.

[Comparative Example 5]
Comparative Example as in Example 1 except that about 30 wt% fine particle dispersion w-21 having an average volume particle diameter of 18 nm is added in an amount of 0.01 part by weight after the emulsification or dispersion process. A toner of 5 was obtained.

[Comparative Example 6]
Comparative Example as in Example 1 except that about 30 wt% fine particle dispersion w-22 having an average volume particle size of 10 nm is added in an amount of 0.01 part by weight after the emulsification or dispersion process. 6 toner was obtained.

[Comparative Example 7]
About 30 wt% fine particle dispersion w-5 having an average volume particle size of 230 nm was added in an amount of 0.50 parts by weight when the aqueous phase was prepared. Thereafter, the fine particle dispersion w-5 is not added after the emulsification or dispersion step. Otherwise, the toner of Comparative Example 7 was obtained in the same manner as in Example 1.

The toners of Examples 1 to 16 and Comparative Examples 1 to 7 were evaluated by the following methods.
The evaluation results are shown in Tables 3 and 4.

(Fine powder content)
The fine powder content is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (dry well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) for about 1 to 3 minutes to obtain a dispersion concentration of 3,000 to 10,000 / μl. To measure the shape and distribution of the resin particles.

(Subduction depth)
As for the depth of subsidence (degree of subsidence), the degree of subsidence of resin fine particles was measured for a sample in which the diameter of the cross section of the toner was within a range of 3-8 μm by a transmission electron microscope (TEM).
At that time, the number of samples was 30.

(Image density)
Using a tandem color electrophotographic apparatus (imagio Neo 450, manufactured by Ricoh Co., Ltd.), the amount of each developer adhered to copy paper (TYPE 6000 <70W>, manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.05 mg / A solid image of cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C.
The image density of arbitrary six places in the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite), and evaluation was performed based on the following evaluation criteria.
The image density value is shown as an average value of image densities at six locations.

(Cleanability)
Transfer residual toner on the photosensitive member that has passed through the cleaning process is transferred to a white paper using a scotch tape (manufactured by Sumitomo 3M Limited), measured with a Macbeth reflection densitometer (RD514 type), and based on the following criteria: The cleaning property was evaluated.
〔Evaluation criteria〕
A (very good): The difference from the blank is less than 0.005.
○ (Good): The difference from the blank is 0.005 or more and 0.01 or less.
X (defect): The difference with a blank exceeds 0.01.

(Skin dirt)
Using an image forming apparatus (“Imagio Neo450”, manufactured by Ricoh Co., Ltd.), a blank paper image is stopped during development, the developer on the photoconductor after development is transferred to the tape, and the image density of the untransferred tape is measured. The difference was measured with a spectrometer (“938 Spectrodensitometer”, manufactured by X-Light).

(Filming)
The presence or absence of toner filming on the developing roller or the photoreceptor was visually observed and evaluated based on the following criteria.
[Evaluation criteria] ○: Filming is not observed.
Δ: Streaky filming is observed.
X: Filming is observed as a whole.

Ａは微粒子の直径を意味する。

A means the diameter of the fine particles.

<Comprehensive evaluation>
From the above evaluation results, a comprehensive judgment was made and the evaluation was made according to the following criteria.
〔Evaluation criteria〕
◎: Very good ○: Good ×: Bad

表４より、実施例１〜１６の現像剤は、比較例１〜７の現像剤と比較して、クリーニング性、地肌汚れ、及びフィルミングにおいて良好な結果が得られた。

From Table 4, the developer of Examples 1-16 obtained the favorable result in cleaning property, background dirt, and filming compared with the developer of Comparative Examples 1-7.

Since the toner of the present invention has a uniform particle size and excellent cleaning properties, it is suitably used for high-quality image formation. A developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner of the present invention are a full color copying machine, a full color laser printer, and a full color using a direct or indirect electrophotographic multicolor image developing system. Can be widely used for plain paper fax machines.

10 Photoconductor (Photoconductor drum)
10K electrostatic latent image carrier for black 10Y electrostatic latent image carrier for yellow 10M electrostatic latent image carrier for magenta 10C electrostatic latent image carrier for cyan 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Sheet reversing apparatus 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 44Y developing roller 44M developing roller 44C developing roller 45K black developing unit 45Y yellow developing unit 45M magenta developing unit 45C cyan developing unit 49 registration roller 50 intermediate transfer member 51 roller 52 corona charger 53 constant current source 55 switching claw 56 Ejection roller 57 Ejection tray 58 Separation roller 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Electrification device 70 Electrification lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 120 Tandem type development device 130 Document table 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 148 paper feed path 150 copier main body 200 paper feed table 300 scanner 400 original Automatic transfer device (ADF)

JP 2008-262179 A

Claims (12)

A toner comprising at least a binder resin, a colorant and a release agent, and granulated in an aqueous medium, wherein the binder resin comprises an amorphous polyester resin containing a polyhydroxycarboxylic acid skeleton in the main chain. The resin fine particles are embedded and fixed on the surface of the toner base particles within a range of the subsidence A / 5 to 2A / 3 (where A represents the diameter of the resin fine particles). Toner.   The toner according to claim 1, wherein the resin fine particles are polyester resin fine particles having a volume average particle diameter of 20 nm or more and 500 nm or less.   The toner according to claim 1, wherein A> B> 0 is satisfied, where A is the diameter of the fine particles and B is the depth of penetration of the fine particles into the toner base.   The volume average particle diameter is 3 μm or more and 8 μm or less, the fine powder content is 15% or less with the number average particle diameter being 2.0 μm or less, and the volume average particle diameter (Dv) and the number average particle diameter (Dn) are The toner according to claim 1, wherein a ratio (Dv / Dn) of the toner is 1.15 or less. The binder resin has an amorphous polyhydroxycarboxylic acid skeleton and a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and an optical purity X (%) represented by the following formula (1) is 80. The toner according to claim 1, wherein the toner is a binder resin characterized by being not more than%.
Optical purity X (%) = | X (L form) -X (D form) | ... Formula (1)
[However, X (L-form) represents the L-form ratio (mol%) contained in the non-crystalline polyester resin in terms of optically active monomer, and X (D-form) represents the non-formity in terms of optically active monomer. The D-form ratio (mol%) contained in crystalline polyester resin is represented. ]   The toner according to claim 1, wherein the amorphous polyhydroxycarboxylic acid skeleton is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms.   The toner according to claim 1, wherein the binder resin contains a linear polyester diol containing a polyhydroxycarboxylic acid skeleton. Developer having a toner and a carrier according to any one of claims 1-7. A developer container, wherein the developer according to claim 8 is accommodated. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with a developer to form a visible image An image forming apparatus having at least a developing unit to form, a transferring unit for transferring the visible image to a recording medium, and a fixing unit for fixing the transferred image transferred to the recording medium, wherein the developer is An image forming apparatus comprising the developer according to claim 8 . An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image bearing member, a visible image by developing with a toner according to the electrostatic latent image to claim 1-7 An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. An image forming apparatus main body having at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image A process cartridge that is attachable to and detachable from the camera, wherein the developer is the developer according to claim 8 .

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