JP2015075742A - Toner for electrophotographic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrophotographic devices that can suppress the occurrence of VOC from an electrophotographic device for a long period.SOLUTION: There is provided a toner for electrophotographic devices that includes toner particles, and particulate allophane having a volume average particle diameter of 0.5 μm or less attached to the surface of each of the toner particles, where the amount of the particulate allophane added is 0.01 parts by mass or more based on 100 parts by mass of the toner particles.

Description

  The present invention relates to a toner for an electrophotographic apparatus, and more particularly, to a toner for an electrophotographic apparatus used in an electrophotographic apparatus such as a copying machine, a printer, a facsimile, or a composite machine using an electrophotographic system.

  In an electrophotographic apparatus such as a copying machine using an electrophotographic method, a resin component mixed in a toner or a coating material (silicone oil, etc.) of a fixing roller is evaporated by being heated to a high temperature by the fixing apparatus. Then, volatile organic compounds (VOC) are generated.

  This VOC is unpleasant in odor and may damage your health, so the emission amount is strictly regulated by the German environmental label system Blue Angel Mark (BAM). It is necessary to reduce emissions.

  Therefore, in order to solve these VOC problems, an electrophotographic dry developer (Patent Document 1) in which a fragrance or activated carbon is added to a toner, or an image forming apparatus in which a filter for removing VOC is disposed in an exhaust duct from fixing. (Patent Document 2) has been proposed.

  However, as described in Patent Document 1, even if a fragrance or activated carbon is added to the toner, the VOC emission cannot be reduced sufficiently. In addition, when activated carbon is added to the toner, the toner is colored, so that it cannot be used for a color toner.

  Moreover, in patent document 2, since there exists a possibility that a filter may deteriorate with time if it uses for a long time, there exists room for improvement in the point which suppresses generation | occurrence | production of VOC for a long time.

JP-A-4-338970 JP 2007-264549 A

  The present invention has been made in view of such circumstances, and an object thereof is to provide a toner for an electrophotographic apparatus that can suppress the generation of VOC from the electrophotographic apparatus for a long period of time.

  The present inventor has conducted extensive research on toners for electrophotographic apparatus that can suppress the generation of VOC from the electrophotographic apparatus for a long period of time. In the course of that research, we focused on allophane, a porous and non-crystalline silica-alumina mineral produced by long-term weathering of volcanic ash soil, and classified and pulverized it into particulate allophane. I thought that VOC could be adsorbed by the porous pores of the particulate allophane when the toner particles were not simply contained (internally added) in the toner particles but adhered (externally added) to the surface of the toner particles. . As a result of repeated experiments on the volume average particle diameter and the external addition amount (addition amount) of the particulate allophane, 0.01 parts by weight of the particulate allophane having a volume average particle diameter of 0.5 μm or less is 0.01 parts by mass. It has been found that the use of externally added toner particles in a proportion of not less than part by mass can suppress the generation of VOC from the electrophotographic apparatus for a long period of time, and has reached the present invention.

  That is, according to the present invention, particulate allophane having a volume average particle diameter of 0.5 μm or less adheres to the surface of the toner particles, and the amount of the particulate allophane added is 0.1% relative to 100 parts by mass of the toner particles. The gist of the toner for an electrophotographic apparatus is 01 parts by mass or more.

  According to the present invention, the VOC generated from the toner and the fixing member at the time of fixing is adsorbed by the porous pores of the particulate allophane externally added to the surface of the toner particles, so that the VOC is generated from the electrophotographic apparatus. Can be suppressed for a long time, and it is not necessary to arrange a filter for removing VOC in the exhaust duct. Moreover, since the particulate allophane is almost colorless and transparent, the toner is not colored like activated carbon, and the hue of the toner is not changed.

  Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.

  The toner for an electrophotographic apparatus of the present invention is obtained by adhering (externally adding) particulate allophane having a volume average particle diameter of 0.5 μm or less to the surface of toner particles. It is the characteristic that it is 0.01 mass part or more with respect to 100 mass parts.

[Particulate allophane]
The particulate allophane used in the present invention (hereinafter abbreviated as “allophane” as appropriate) needs to have a volume average particle diameter of 0.5 μm or less. If the volume average particle diameter of allophane is too large, the adhesion force to the toner particles is small, and allophane is detached from the surface of the toner particles, so that the VOC adsorption ability of the toner may be inferior.

  On the other hand, if the volume average particle diameter of the allophane is too small, the surface area of the allophane increases and the toner charging tends to be affected. Therefore, the lower limit of the volume average particle diameter of the allophane is 0.2 μm or more. Is preferred.

  In the present invention, the volume average particle diameter of the allophane needs to be 0.5 μm or less, and preferably in the range of 0.2 to 0.5 μm.

  In addition, the volume average particle diameter of the allophane can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (LA-920, manufactured by Horiba, Ltd.).

  As described above, allophane is a porous, non-crystalline silica-alumina mineral produced by weathering volcanic ash soil for a long period of time. In order to obtain particulate allophane having a desired volume average particle size, it is necessary to adjust the particle size by classifying or pulverizing and classifying raw materials containing allophane as necessary.

  The shape of the particulate allophane used in the present invention is not limited to a spherical shape, and may be a hemispherical shape.

  In the present invention, the addition amount (external addition amount) of allophane to the toner particle surface needs to be 0.01 parts by mass or more with respect to 100 parts by mass of the toner particles. When the amount of allophane added is too small, the adsorption capacity of VOC is poor.

  On the other hand, since allophane is a porous material that easily absorbs moisture, if the amount of allophane added is too large, it tends to be affected by atmospheric humidity, and the charge amount of the toner tends to change from a desired value. Therefore, the upper limit of the amount of allophane added is preferably 0.2 parts by mass or less with respect to 100 parts by mass of the toner particles.

  The addition amount (external addition amount) of the allophane in the present invention needs to be 0.01 parts by mass or more, preferably 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the toner particles. Within the range, particularly preferably within the range of 0.1 to 0.2 parts by mass.

  The toner for an electrophotographic apparatus of the present invention can be usually produced by a pulverization classification method, a melt granulation method, a spray granulation method, a polymerization method or the like, and the pulverization classification method is preferable. In this pulverization and classification method, toner components such as a binder resin, a colorant, a charge control agent, wax, and a magnetic material (magnetic powder) are mixed in advance by a mixer such as a Henschel mixer, and then a twin screw extruder or the like. The toner particles can be produced by kneading using a kneading apparatus, cooling, pulverizing and classifying.

  The volume average particle diameter of the toner particles is preferably in the range of 5 to 20 μm. The volume average particle diameter can be measured using, for example, Multisizer 3 (manufactured by Beckman Coulter, Inc.).

  Next, to the toner particles obtained as described above, by adding particulate allophane having a volume average particle diameter of 0.5 μm or less as an external additive, and if necessary, other external additives. Thus, a toner for an electrophotographic apparatus can be obtained.

[Binder resin]
Examples of the binder resin include thermoplastic resins and thermosetting resins, and thermoplastic resins are preferably used.

(Thermoplastic resin)
Examples of the thermoplastic resin include styrene resins, acrylic resins, styrene-acrylic copolymers, polyethylene resins, polypropylene resins, vinyl chloride resins, polyester resins, polyamide resins, polyurethane resins, Examples thereof include polyvinyl alcohol resins, vinyl ether resins, N-vinyl resins, and styrene-butadiene resins. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The styrenic resin may be a homopolymer of a styrene monomer or a copolymer with another copolymerizable monomer copolymerizable with the styrene monomer. Examples of the copolymerization monomer include p-chlorostyrene; vinyl naphthalene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl halides such as vinyl chloride, vinyl bromide, and vinyl fluoride; vinyl acetate. , Vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, n-octyl acrylate, 2-chloroethyl acrylate , (Meth) acrylic esters such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate; other acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide Conductors: Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrole N-vinyl compounds such as den. These may be used alone or in combination of two or more with a styrene monomer.

  Examples of the polyester resin include those obtained by condensation polymerization or co-condensation polymerization of a divalent or trivalent or higher alcohol component and a divalent or trivalent or higher carboxylic acid component.

  Examples of the divalent or trivalent or higher alcohol component include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1 Diols such as 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; bisphenol A, Bisphenols such as hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A; sorbitol, 1,2,3,6-hexanetetrol, 1,4-so Vitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2, Examples thereof include trivalent or higher alcohols such as 4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

  Further, as the divalent or trivalent or higher carboxylic acid component, divalent or trivalent or higher carboxylic acids, acid anhydrides thereof, or lower alkyl esters thereof are used. For example, maleic acid, fumaric acid ( Fumaric acid), citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or n-butylsuccinic acid, n-butenylsuccinic acid Acids, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid alkyl or alkenyl succinic acid Divalent carboxylic acids such as acids; 1,2,4-benzene Carboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1, 2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8- Examples thereof include octanetetracarboxylic acid, pyromellitic acid, and emporic trimer acid trivalent or higher carboxylic acid.

(Thermosetting resin)
Examples of the thermosetting resin include an epoxy resin and an anate resin, and specifically, a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a novolac type epoxy resin, and a polyalkylene ether type. Examples thereof include an epoxy resin, a cycloaliphatic epoxy resin, and a cyanate resin. These may be used individually by 1 type and may be used in combination of 2 or more type.

[Colorant]
Examples of the colorant include black pigments, yellow pigments, orange pigments, red pigments, purple pigments, blue pigments, green pigments, and white pigments. Examples of the black pigment include carbon black such as acetylene black, run black (oil smoke), and aniline black. Examples of the yellow pigment include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine. Yellow GR, quinoline yellow rake, permanent yellow NCG, tartrazine rake and the like. Examples of the orange pigment include reddish yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK. Examples of the red pigment include bengara, cadmium red, red lead, mercury cadmium sulfide, permanent red 4R, risor red, pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B. , Alizarin lake, brilliant carmine 3B and the like. Examples of the violet pigment include manganese violet, fast violet B, and methyl violet lake. Examples of the blue pigment include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated product, first sky blue, and induslen blue BC. Examples of the green pigment include chrome green, chromium oxide, pigment green B, malachite green lake, and final yellow green G. Examples of the white pigment include zinc white, titanium oxide, antimony white, zinc sulfide, barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  The blending amount of the colorant is preferably in the range of 2 to 20 parts by mass and more preferably in the range of 5 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

(Charge control agent)
The charge control agent is blended in order to remarkably improve the charge level and charge rising characteristics (indicator of whether to charge to a constant charge level in a short time), and to obtain characteristics excellent in durability and stability. Is. That is, when the toner is positively charged for development, a positively chargeable charge control agent is added. When the toner is negatively charged for development, a negatively chargeable charge control agent can be added. .

  Examples of the positively chargeable charge control agent include pyridazine, pyrimidine, pyrazine, orthooxazine, metaoxazine, paraoxazine, orthothiazine, metathiazine, parathiazine, 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, 1,2,4-oxadiazine, 1,3,4-oxadiazine, 1,2,6-oxadiazine, 1,3,4-thiadiazine, 1,3,5-thiadiazine, 1, 2,3,4-tetrazine, 1,2,4,5-tetrazine, 1,2,3,5-tetrazine, 1,2,4,6-oxatriazine, 1,3,4,5-oxatriazine, Azine compounds such as phthalazine, quinazoline, quinoxaline; azine fast red FC, azine fast red 12BK, azine violet BO, Direct dyes composed of azine compounds such as gin brown 3G, azine light brown GR, azine dark green BH / C, azine deep black EW, azine black 3RL; nigrosine compounds such as nigrosine, nigrosine salt, nigrosine derivatives; nigrosine BK, nigrosine Examples include acidic dyes composed of nigrosine compounds such as NB and nigrosine Z; metal salts of naphthenic acid or higher fatty acids; alkoxylated amines; alkylamides; quaternary ammonium salts such as benzylmethylhexyldecylammonium and decyltrimethylammonium chloride. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, a nigrosine compound is preferably used from the viewpoint of obtaining a quicker charge rising property.

  Examples of the positively chargeable charge control agent include styrenic resins, acrylic resins, styrene-acrylic resins, polyester resins having functional groups such as quaternary ammonium salts, carboxylates, and carboxyl groups. These resins can also be used.

  On the other hand, as the charge control agent exhibiting negative chargeability, an organometallic complex, a chelate compound and the like are preferable. Specific examples include aluminum acetylacetonate, iron (II) acetylacetonate, 3,5-di-tert- Examples thereof include chromium butylsalicylate. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, acetylacetone metal complexes, salicylic acid metal complexes or salicylic acid metal salts are preferable, and salicylic acid metal complexes or salicylic acid metal salts are particularly preferable.

  The blending amount of the charge control agent is preferably in the range of 1.5 to 15 parts by mass, and in the range of 1.5 to 8 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is particularly preferably in the range of 1.5 to 7 parts by mass.

  In addition, without using the charge control agent, the binder resin may have a part of the charge control action. For example, as part of the binder resin, a cationic or anionic polar group It is also possible to use a copolymer having Examples of the cationic polar group include bases such as primary, secondary or tertiary amino groups, quaternary ammonium groups, amide groups, imino groups, imide groups, hydrazino groups, guanidino groups, and amidino groups. Reactive nitrogen-containing groups. Examples of the anionic polar group include polar groups such as carboxylic acid, sulfonic acid, and phosphonic acid. Examples of the resin having the charge control function include, for example, a cationic or anionic polar group-containing monomer, random copolymerization with other monomers or resins, block copolymerization, graft copolymerization, and the like. And a resin polymerized in (1).

[Wax (release agent)]
The wax is used to improve fixability and offset resistance. For example, polyethylene wax, polypropylene wax, polytetrafluoroethylene (PTFE) wax, Fischer-Tropsch wax, paraffin wax, ester wax, montan wax, rice For example, wax. These may be used individually by 1 type and may be used in combination of 2 or more type. By using such a wax, it becomes possible to more effectively prevent offset and image smearing (dirt around the image when the image is rubbed).

  The blending amount of the wax is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

(External additive)
In the toner for an electrophotographic apparatus of the present invention, an external additive other than allophane may be used in combination with the allophane. Examples of such external additives include inorganic metal oxides such as titanium oxide, alumina, magnesium oxide, zinc oxide, strontium titanate, and barium titanate. These may be used individually by 1 type and may be used in combination of 2 or more type. By treating the surface of the toner particles with these external additives, the fluidity, storage stability, cleaning properties, etc. of the toner can be improved.

  Further, in addition to the inorganic metal oxide, fine particles (usually having an average particle size of 1.0 μm or less) for imparting fluidity and polishing properties such as silica (colloidal silica, hydrophobic silica) are externally added. You can also.

  The amount of these external additives is preferably in the range of 0.2 to 100 parts by mass with respect to 100 parts by mass of the toner particles. In order to reduce the frictional resistance with the photoreceptor, for example, an external additive such as zinc stearate is blended within a range of 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the toner particles. It doesn't matter.

  The toner for an electrophotographic apparatus of the present invention can be applied to all types of toner for developing an electrostatic latent image. Specifically, it can be applied regardless of a one-component developer or a two-component developer.

[Carrier]
The toner for electrophotographic apparatus of the present invention can be mixed with a desired carrier and used as a two-component developer. As the carrier, a magnetic carrier is preferably used.

  Examples of the magnetic carrier include magnetic particles and a so-called coating carrier in which the magnetic particles are coated with a resin.

  Examples of the material of the magnetic particles include magnetic metals such as iron, nickel and cobalt, and alloys thereof, alloys containing rare earths, hematite, magnetite, manganese-zinc ferrite, nickel-zinc ferrite Examples thereof include soft ferrites such as manganese-magnesium ferrite and lithium ferrite, iron-based oxides such as copper-zinc ferrite, and mixtures thereof. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the resin for coating the magnetic particles include silicone resins such as methyl silicone and methyl phenyl silicone; fluorine such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, monochlorotrifluoroethylene, monochloroethylene, and trifluoroethylene. Resin; (meth) acrylic resin such as methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate; styrene resin such as styrene, chlorostyrene, methylstyrene; styrene-acrylic resin; polyester resin A polyamide-based resin; These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, silicone resins and fluorine resins are preferable in terms of durability and spent resistance.

  The volume average particle diameter of the carrier is usually in the range of 20 to 100 μm. The average particle diameter of the carrier can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (for example, LA-920 manufactured by Horiba, Ltd.).

The apparent density of the carrier varies depending on the carrier composition and surface structure, but is usually in the range of 2.4 × 10 ^{3 to} 3.0 × 10 ³ kg / m ³ .

  When the toner for an electrophotographic apparatus of the present invention is used as a two-component developer, the toner content is usually in the range of 1 to 20% by weight with respect to the weight of the two-component developer, preferably 3 to It is in the range of 15% by weight. By keeping the toner content in the two-component developer within the above range, it is possible to maintain an appropriate image density, and to suppress the toner scattering and the toner adhesion inside the image forming apparatus and the transfer paper. Can do.

  The toner for an electrophotographic apparatus of the present invention can also be used as a non-magnetic one-component developer or a magnetic one-component developer by adding a magnetic material (magnetic powder) to toner particles. As the magnetic material, the same material as the magnetic material used for the magnetic carrier can be used.

  In the toner for electrophotographic apparatus of the present invention, particulate allophane is adhered (externally added) to the surface of the toner particles. Therefore, even when magnetic toner is produced, the particulate allophane is pulverized with a magnetic material (magnetic powder) or the like. Therefore, the VOC adsorption function can be fully exhibited.

Next, examples of the present invention will be described together with comparative examples. However, the present invention is not limited to these examples.
First, prior to the examples and comparative examples, the following materials were prepared.

[Preparation of allophane a]
The raw material containing allophane (volcanic ash soil) and water were mixed and allowed to settle, and then the supernatant was dried and ground to obtain allophane. This allophane was further pulverized and classified to prepare particulate allophane a (for Examples) having a volume average particle diameter of 0.2 μm.
In addition, a laser diffraction / scattering type particle size distribution measuring device (manufactured by Horiba, Ltd., LA-920) was used for measuring the volume average particle size.

[Production of allophane b and c]
In accordance with the production of allophane a, particulate allophane b (for Examples) and allophane c (for Comparative Examples) having different volume average particle diameters were produced (see Table 1).

[Production of toner particles (toner powder) A]
100 parts by weight of binder resin (styrene-acrylic resin), 4 parts by weight of wax (release agent), 12 parts by weight of colorant (carbon black) and 1 part by weight of charge control agent (nigrosine), a Henschel mixer The mixture was dispersed and mixed, melt-kneaded with a twin-screw kneader, and cooled with a drum flaker. Next, after roughly pulverizing with a hammer mill, finely pulverizing with a turbo mill, and classifying with an air classifier, the volume average particle diameter is 7.0 μm, 10 μm or more is 2.0% by volume, and 3 μm or less is 1 0% by volume of toner particles (toner raw powder) A was produced.

[Example 1]
1. 100 parts by mass of toner particles A, 0.10 parts by mass of allophane a (see Table 1), 0.5 parts by mass of silica particles (REA200, manufactured by Nippon Aerosil Co., Ltd.), titanium oxide particles (manufactured by Teika, JR-405) 5 parts by mass was added and mixed with a Henschel mixer at 3000 rpm for 10 minutes to prepare a toner.

[Examples 2 to 4, Comparative Examples 1 and 2]
Various toners were prepared in the same manner as in Example 1 except that the type and addition amount of allophane of Example 1 were changed as shown in Table 2 below. In Comparative Example 1, no allophane was added.

  Using the toners of Examples 1 to 4 and Comparative Examples 1 and 2 obtained above, the VOC concentration was calculated and evaluated according to the following criteria. The results are shown in Table 2 above.

[Measurement of VOC concentration]
The toner produced in Examples 1 to 4 and Comparative Examples 1 and 2 was set in a multifunction machine (manufactured by Kyocera Document Solutions, “TASKalfa 4500i”), and installed in a chamber having a volume of 5 m ^{3 that} can be ventilated. Image formation was continuously performed for 20 minutes while ventilating at ³ / h, and then left for 80 minutes in a standby state where image formation was not performed. Next, air in the chamber was collected in a Tenax tube at a rate of 0.1 L / min, and gas components adsorbed on the Tenax tube were analyzed using a gas chromatograph mass spectrometer (GC-MS device). And the organic gas component which appears between n-hexane and n-hexadecane was quantified, VOC density | concentration was computed and evaluated. Evaluation, VOC concentration × those 150 [mu] g / ^{m 3} or more, VOC concentration of ○ a of less than 150 [mu] g / ^{m 3.}

  From the results of Table 2, Examples 1 to 4 use allophane having a volume average particle diameter of 0.5 μm or less, and the allophane addition amount is 0.01 parts by mass with respect to 100 parts by mass of the toner particles. Because of the above, the VOC concentration was low, and the generation of VOC could be suppressed for a long time.

  On the other hand, in Comparative Example 1, since allophane was not externally added, the VOC concentration was extremely high, and generation of VOC could not be suppressed at all.

  Further, in Comparative Example 2 in which the volume average particle diameter of allophane is too large, the adhesion force to the toner particles is small, the allophane is detached from the surface of the toner particles, and the VOC adsorption ability is inferior. Occurrence could not be suppressed for a long time.

  Therefore, in order to suppress the generation of VOC for a long period of time, allophane having a volume average particle diameter of 0.5 μm or less is used, and the amount of allophane added is 0.01 mass with respect to 100 mass parts of the toner particles. It was confirmed that more than part was necessary.

  As a result of performing image confirmation using Example 3 and Example 4, Example 3 in which the allophane content is 0.2 parts by mass is an example in which the allophane content exceeds 0.2 parts by mass. Compared with 4, toner chargeability was excellent. That is, it was found that the allophane content is preferably 0.2 parts by mass or less from the viewpoint of toner chargeability.

[Preparation of magnetic toner particles (magnetic toner raw powder) B]
Magnetic toner particles (magnetic toner raw powder) B were produced in substantially the same manner as toner particles A, except that magnetic powder was added instead of the colorant (carbon black). That is, 100 parts by mass of binder resin (styrene-acrylic resin), 80 parts by mass of magnetic powder (ferrite), 4 parts by mass of wax (release agent) and 1 part by mass of charge control agent (nigrosine) were mixed with a Henschel mixer. Were dispersed and mixed, melt-kneaded with a twin-screw kneader, and cooled with a drum flaker. Next, after roughly pulverizing with a hammer mill, finely pulverizing with a turbo mill, and classifying with an air classifier, the volume average particle diameter is 7.0 μm, 10 μm or more is 2.0% by volume, and 3 μm or less is 1 0.0% by volume of magnetic toner particles (magnetic toner raw powder) B was prepared.

Example 5
A toner was prepared in the same manner as in Example 1 except that magnetic toner particles (magnetic toner raw powder) B were used instead of toner particles (toner raw powder) A. That is, 100 parts by mass of magnetic toner particles B, 0.10 parts by mass of allophane a (see Table 1), 0.5 parts by mass of silica particles (manufactured by Nippon Aerosil Co., Ltd., REA200), titanium oxide particles (manufactured by Teika Co., Ltd., JR- 405) 1.5 parts by mass was added and mixed with a Henschel mixer at 3000 rpm for 10 minutes to produce a magnetic toner.

[Examples 6 to 8, Comparative Examples 3 and 4]
Various magnetic toners were prepared in the same manner as in Example 5 except that the type and addition amount of allophane of Example 5 were changed as shown in Table 3 below. In Comparative Example 3, no allophane was added.

  Using the toners of Examples 5 to 8 and Comparative Examples 3 and 4 obtained above, the VOC concentration was calculated and evaluated according to the following criteria. The results are shown in Table 3 above.

[Measurement of VOC concentration]
The VOC concentration is the same as the VOC concentration measurement except that a multifunction device (Kyocera Document Solutions, “TASKalfa 520i”) is used instead of the multifunction device (Kyocera Document Solutions, “TASKalfa 4500i”). Was measured. In other words, the magnetic toner produced in Examples 5 to 8 and Comparative Examples 3 and 4 was set in a multi-function machine (manufactured by Kyocera Document Solutions, “TASKalfa 520i”), and installed in a chamber with a volume of 5 m ^{3 that} can be ventilated. Then, image formation was continuously performed for 20 minutes while ventilating at 15 m ³ / h, and then left for 80 minutes in a standby state where image formation was not performed. Next, the air in the chamber was collected in a Tenax tube at a rate of 0.1 L / min, and the gas component adsorbed on the Tenax tube was analyzed using a GC-MS apparatus. And the organic gas component which appears between n-hexane and n-hexadecane was quantified, VOC density | concentration was computed and evaluated. Evaluation, VOC concentration × those 150 [mu] g / ^{m 3} or more, VOC concentration of ○ a of less than 150 [mu] g / ^{m 3.}

  From the results of Table 3, Examples 5 to 8 use allophane having a volume average particle diameter of 0.5 μm or less, and the allophane addition amount is 0.01 parts by mass with respect to 100 parts by mass of the toner particles. Because of the above, the VOC concentration was low, and the generation of VOC could be suppressed for a long time.

  On the other hand, in Comparative Example 3, since allophane was not externally added, the VOC concentration was extremely high, and the generation of VOC could not be suppressed at all.

  Further, in Comparative Example 4 in which the volume average particle diameter of allophane is too large, the adhesion force to the toner particles is small, the allophane is detached from the surface of the toner particles, and the VOC adsorption ability is inferior. Occurrence could not be suppressed for a long time.

  Therefore, in order to suppress the generation of VOC for a long period of time, allophane having a volume average particle diameter of 0.5 μm or less is used, and the amount of allophane added is 0.01 mass with respect to 100 mass parts of the toner particles. It was confirmed that more than part was necessary.

  In addition, as a result of performing image confirmation using Example 7 and Example 8, Example 7 in which the content of allophane is 0.2 parts by mass is an example in which the content of allophane exceeds 0.2 parts by mass. Compared to 8, the toner chargeability was excellent. That is, it was found that the allophane content is preferably 0.2 parts by mass or less from the viewpoint of toner chargeability.

  The toner for an electrophotographic apparatus of the present invention can be used as a toner for an electrophotographic apparatus such as a copying machine, a printer, a facsimile, or a complex machine using an electrophotographic system.

Claims (4)

  Particulate allophane having a volume average particle diameter of 0.5 μm or less adheres to the surface of the toner particles, and the amount of the particulate allophane added is 0.01 parts by mass or more with respect to 100 parts by mass of the toner particles. A toner for an electrophotographic apparatus.   The toner for an electrophotographic apparatus according to claim 1, wherein the toner particles contain a magnetic material.   The toner for an electrophotographic apparatus according to claim 1, wherein the amount of particulate allophane added is 0.2 parts by mass or less with respect to 100 parts by mass of the toner particles.   The toner for an electrophotographic apparatus according to claim 1, wherein the volume average particle diameter of the particulate allophane is 0.2 μm or more.