JP5396523B2 - Developer - Google Patents

Description

  The present invention relates to a developer used in an electrophotographic apparatus such as a copying machine, a printer, a facsimile, or a composite machine using the electrophotographic method, and more specifically, development for the purpose of preventing forgery by the electrophotographic apparatus. It relates to the agent.

  Conventionally, with the colorization of copiers, it has become possible to copy specific manuscripts that should not be originally copied (for example, banknotes, securities, etc.) with high image quality that is almost indistinguishable from the actual product. Things are often abused. In the case of such misuse, if the copier that made the copy or the person who made the copy can be identified, the forged person can be easily identified, and as a result, forgery can be prevented. it can.

  For this purpose, a copying machine having a function of adding a specific pattern to a copy image such as a bill has been proposed (for example, see Patent Document 1). This function is used to create a specific pattern (such as information useful for identifying the device used for copying (for example, a device-specific serial number or this). ) And information useful for identifying the copied person (for example, a recognized ID number in a copier that requires input of an ID number when used, or encoding this) Etc.))] is added.

  However, in the prior art, in order to ensure that a specific pattern is formed in a copy image such as a banknote, it is necessary to form a specific pattern with yellow toner also in a non-image area of the printing paper. This results in wasteful consumption of yellow toner. Further, in order to form a specific pattern using yellow toner, a copying machine having a corresponding function is required.

JP-A-4-294682

  SUMMARY OF THE INVENTION An object of the present invention is to provide a developer that achieves anti-counterfeiting in an electrophotographic apparatus without wastefully consuming toner for a general user and without requiring special apparatus modification.

  As a result of intensive studies in order to solve the above problems, the present inventor includes a developer containing toner containing fine particles mainly composed of resin, and forms identification marks such as letters, symbols, and figures. Thus, it has been found that forgery prevention can be achieved without wastefully consuming toner and without requiring special device modification, and the present invention has been completed.

(1) A developer containing at least a toner for use in an electrophotographic apparatus, containing fine particles mainly containing a resin in addition to the toner, and having an identification mark formed on the fine particles. The glass transition temperature Tg1 (° C.) of the resin, which is a main component of the fine particles, and the glass transition temperature Tg2 (° C.) of the binder resin in the toner are Tg2 <Tg1 <(Tg2 + 10). And a developer having the following relationship:
(2) A developer containing at least a toner for use in an electrophotographic apparatus, containing fine particles mainly containing a resin in addition to the toner, and an identification mark formed on the fine particles, A melting point Tm1 (° C.) of the resin, which is a main component of the fine particles, and a melting point Tm2 (° C.) of the binder resin in the toner have a relationship of Tm2 <Tm1 <(Tm2 + 10). A developer characterized by comprising:
(3) The developer according to claim 1 or 2, comprising 0.1 to 15 parts by weight of the fine particles with respect to 100 parts by weight of the toner.

  According to the present invention, in a developer used in an electrophotographic apparatus such as a copying machine, printing is performed using this developer by causing the toner to contain fine particles on which identification marks such as characters, symbols, and figures are formed. The fine particles are also present in the toner image. Therefore, when there is a possibility of a counterfeit bill, an image is observed with an optical microscope, and if the identification mark is confirmed in the image, it is easily determined that the copy is a bill copy. As identification marks formed on the fine particles, information useful for identifying the device used for copying (for example, a device-specific serial number or an encoded number thereof), or for identifying a copied person Displaying information (for example, a recognized ID number in a copier or the like that requires input of an ID number at the time of use) It is possible to specify anti-counterfeiting and achieve counterfeit prevention. Further, by using a developer containing such specific fine particles, forgery of the developer itself can be prevented.

  In the formation of a copy image using the developer of the present invention, since toner containing fine particles is applied only to the image portion, a specific pattern with yellow toner is formed on the white paper portion of the printing paper in the prior art, There is no need to waste toner. Further, the image formation using the developer of the present invention can be carried out by a normal copying machine or the like, and does not require any special device modification.

  The developer of the present invention is a developer containing at least a toner used in an electrophotographic apparatus. The developer contains specific fine particles in addition to the toner. That is, since the developer of the present invention has a configuration in which specific fine particles are contained in the developer containing toner, it can be applied to all types of developers for developing electrostatic latent images.

  Specifically, it can be applied regardless of a dry developer (a toner or a mixture of toner and carrier as it is) or a wet developer (a toner dispersed in an electrically insulating liquid). In addition, in dry developers, there are one-component developers (one consisting only of toner, toner includes non-magnetic toner and magnetic toner (one containing a magnetic substance in toner particles)), two-component developer (toner And a carrier, and a carrier includes a magnetic carrier and a non-magnetic carrier).

<Fine particles>
The fine particles of the present invention contain a resin as a main component. As the resin, the same resin as the binder resin used for the toner described later can be used. The fine particles may be colored in a color such as black, yellow, magenta, cyan, etc. as in the toner, but may be uncolored. A charge control agent is preferably used for the fine particles.

  The colorant is used in an amount of 2 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin, which is the main component of the fine particles. The charge control agent is used in a proportion of 1.5 to 15 parts by weight, preferably 1.5 to 8.0 parts by weight, more preferably 1.5 to 7.0 parts by weight with respect to 100 parts by weight of the resin. It is good to do. As these colorant and charge control agent, those similar to those used for the toner described later can be used. In addition to the colorant and the charge control agent, a compounding agent such as a release agent (wax) can be blended with the fine particles.

  Since the fine particles are used in the development process and the fixing process in the same manner as the toner particles, it is preferable that the fine particles have almost the same particle diameter as the toner particles and have almost the same charging performance and fixing performance. Therefore, the fine particles according to the present invention are preferably composed of a resin having substantially the same charging performance and thermal performance as the binder resin in the toner used in combination. However, it is not necessary to use the same or same type of resin as the binder resin of the toner used in combination. It is preferable to use a charge control agent or the like having a performance comparable to that contained in the toner used in combination.

  Here, identification marks such as letters, symbols, and figures are formed on the fine particles. As the identification mark, a desired mark can be adopted. From the viewpoint of preventing counterfeiting, it is preferable to adopt information useful for specifying the device used for copying or information useful for specifying the copied person. .

  Information useful for identifying the device used for copying includes, for example, the device manufacturing country name, manufacturing date, manufacturing lot number, model number, developer manufacturing country name, manufacturing date, manufacturing lot number, manufacturing number, etc. These may be encoded. Information useful for identifying a copied person includes a recognized ID number in a copying machine or the like that requires the input of an ID number at the time of use, or an encoded one.

  The identification mark may be formed on the surface of the fine particles or may be formed inside. When formed inside, the fine particles are preferably transparent or nearly transparent. The identification mark may be planar or three-dimensional. Examples of the planar identification mark include coloring labels. Examples of the three-dimensional identification mark include a stamp. The stamp may be convex, concave, or a combination thereof.

  As the shape of the fine particles, a desired shape can be adopted as long as it becomes spherical by heating, pressurization or the like. That is, as the shape of the fine particles, in addition to a spherical shape, for example, a solid shape such as a hemispherical shape, a rectangular parallelepiped, or a cube can be adopted.

  When the shape of the fine particles is spherical or hemispherical, the volume average particle diameter of the fine particles is preferably about 7 to 25 μm. Moreover, when the shape of the fine particles is a three-dimensional shape, the length of one side (width, length, thickness) is preferably about 5 to 20 μm. If the shape of the fine particles is too small, it becomes difficult to identify the identification mark by a simple method such as an optical microscope. Further, if the shape of the fine particles is too large, uniform dispersion with the toner particles tends to be difficult. The volume average particle diameter of the fine particles can be measured using, for example, Multisizer 3 (manufactured by Beckman Coulter, Inc.). Further, the length of one side of the fine particles can be measured with an optical microscope.

  The toner contains a binder resin, and the glass transition temperature Tg1 (° C.) of the resin, which is a main component of fine particles, and the glass transition temperature Tg2 (° C.) of the binder resin in the toner are Tg2 <Tg1 <. It is preferable to have a relationship (Tg2 + 10) (this relationship may be referred to as relationship I). Thereby, even in an image fixed by heating, pressing, etc., the fine particles are not softened and melted and almost retain their original form, so that the identification mark can be confirmed by observation with an optical microscope or the like. More preferably, (Tg2 + 2) <Tg1 <(Tg2 + 10).

  The glass transition temperature Tg1 is preferably about 35 to 75 ° C, and the glass transition temperature Tg2 is preferably about 30 to 70 ° C. The glass transition temperature can be determined from the change point of specific heat using a differential scanning calorimeter (DSC). Specifically, an endothermic curve is measured using a differential scanning calorimeter “DSC-6200” manufactured by Seiko Instruments Inc. as a measuring device. This endothermic curve is obtained by placing 10 mg of a measurement sample in an aluminum pan, using an empty aluminum pan as a reference, and measuring at a measurement temperature range of 25 to 200 ° C. and a rate of temperature increase of 10 ° C./min. Can be obtained. And glass transition temperature is calculated | required from the obtained endothermic curve.

  On the other hand, if the glass transition temperatures Tg1 and Tg2 are Tg1 ≦ Tg2, the fine particles are melted when the toner is fixed, and the identification mark may not be identified. Further, if Tg1 ≧ (Tg2 + 10), the toner tends to be prevented from being fixed.

  The melting point Tm1 (° C.) of the resin, which is the main component of the fine particles, and the melting point Tm2 (° C.) of the binder resin in the toner have a relationship of Tm2 <Tm1 <(Tm2 + 10). ). Thereby, even in an image fixed by heating, pressing, etc., the fine particles are not softened and melted and almost retain their original form, so that the identification mark can be confirmed by observation with an optical microscope or the like. More preferably, (Tm2 + 2) <Tm1 <(Tm2 + 10). In the present invention, it is more preferable that both the relation I and the relation II are satisfied.

  The melting point Tm1 is preferably about 105 to 145 ° C, and the melting point Tm2 is preferably about 100 to 140 ° C. The melting point can be measured using a differential scanning calorimeter (DCS).

  On the other hand, if the melting points Tm1 and Tm2 are Tm1 ≦ Tm2, the fine particles are melted when the toner is fixed, and the identification mark cannot be identified. Further, if Tm1 ≧ (Tm2 + 10), there is a tendency to prevent toner fixing.

  The developer according to the present invention preferably contains 0.1 to 15 parts by weight of the fine particles with respect to 100 parts by weight of the toner. By making the fine particles 0.1 parts by weight or more with respect to 100 parts by weight of the toner, there is no inconvenience that the fine particles are buried in the toner and cannot be confirmed, and by making the fine particles 15 parts by weight or less, fixing is inhibited. There is nothing.

  The fine particles can be obtained, for example, as follows. That is, first, if necessary, a resin mixed with a colorant, a charge control agent, and other compounding agents is molded by, for example, an extrusion method to produce a resin plate having a thickness similar to the size of toner particles. . Subsequently, the resin plate is punched out to a size similar to that of the toner particles with a mold on which a desired identification mark is imprinted, whereby fine particles having an identification mark formed on the surface are obtained.

  In order to obtain fine particles having an identification mark formed therein, for example, the following method can be employed. That is, first, a resin plate is obtained in the same manner as described above, and the resin plate is punched with a mold not engraved with an identification mark to obtain fine particles on which no identification mark is formed. Subsequently, the fine particles are laminated on the surface of the fine particles having the identification mark formed on the surface obtained above and integrated by heating, pressurizing, etc., thereby obtaining the fine particles having the identification mark formed therein. . In addition, the manufacturing method of microparticles | fine-particles is not limited to above-mentioned, It can manufacture by various methods.

  On the other hand, the developer of the present invention is configured as a one-component developer or a two-component developer using ordinary toner and carrier except that the fine particles are blended. At that time, as described above, it is preferable to mix 0.1 to 15 parts by weight of the fine particles with respect to 100 parts by weight of the toner.

<Toner>
The toner is prepared by dispersing and granulating a colorant, a charge control agent, a wax and the like in a binder resin, and adding an external additive as desired.

(Binder resin)
The binder resin is not particularly limited, but for example, styrene resin, acrylic resin, styrene-acrylic copolymer, polyethylene resin, polypropylene resin, vinyl chloride resin, polyester resin, It is preferable to use thermoplastic resins such as polyamide resins, polyurethane resins, polyvinyl alcohol resins, vinyl ether resins, N-vinyl resins, styrene-butadiene resins.

  The styrene resin may be a styrene homopolymer or a copolymer with another copolymerizable monomer copolymerizable with styrene. 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; Vinyl ethers such as chill ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and methyl isopropenyl ketone; N such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidene -A vinyl compound etc. are mentioned. These may be used alone or in combination of two or more with a styrene monomer.

  Any polyester-based resin can be used as long as it is obtained by condensation polymerization or co-condensation polymerization of an alcohol component and a carboxylic acid component. The following are mentioned as a component used when synthesize | combining a polyester-type resin. First, as a bivalent or trivalent or higher alcohol component, for example, 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-sorbi , Pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-1,2, Examples include trivalent or higher alcohols such as 4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

  As the divalent or trivalent or higher carboxylic acid component, a divalent or trivalent carboxylic acid, an acid anhydride thereof or a lower alkyl ester thereof is 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-butyl succinic acid, n-butenyl succinic acid, isobutyl succinic acid, isobutenyl Divalent carboxylic acids such as alkyl or alkenyl succinic acid such as succinic acid, n-octyl succinic acid, n-octenyl succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid; 1,2,4-benzenetricarboxylic acid (trimellitic acid), , 2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, , 3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Examples thereof include trivalent or higher carboxylic acids such as Empol trimer acid.

  The binder resin may be a thermosetting resin. Thus, by introducing a partially crosslinked structure, it is possible to further improve the storage stability, form retention, and durability of the toner without lowering the fixability. Therefore, it is not necessary to use 100 parts by weight of the thermoplastic resin as the toner binder resin, and it is also preferable to add a cross-linking agent or to partially use a thermosetting resin.

  As the thermosetting resin, an epoxy resin or a cyanate resin may be used. Specifically, one or a combination of two or more of bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, novolac type epoxy resin, polyalkylene ether type epoxy resin, cycloaliphatic type epoxy resin, cyanate resin, etc. Is mentioned.

(Coloring agent)
Examples of the colorant include black pigments such as acetylene black, lanblack, and aniline black; black pigments such as yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, and navel. S Yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake; orange pigment, reddish yellow lead, molybten orange, permanent orange GTR , Pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK; Dome 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; purple pigment As a blue pigment, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, fast sky blue, induslen Blue BC: Chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green as green pigments ; As a white pigment include zinc white, titanium oxide, antimony white, zinc sulfide; as a white pigment, baryta powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like can be used. The colorant is preferably used in a ratio of 2 to 20 parts by weight, particularly 5 to 15 parts by weight, based on 100 parts by weight 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. .

  The charge control agent is not particularly limited, but specific examples of the positively chargeable charge control agent include pyridazine, pyrimidine, pyrazine, orthooxazine, metaoxazine, paraoxazine, orthothiazine, and 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, phthalazine, quinazoline, quinoxaline and other azine compounds; Direct dyes composed of azine compounds such as FC, azine fast red 12BK, azine violet BO, azine brown 3G, azine light brown GR, azine dark green BH / C, azine deep black EW and azine black 3RL; nigrosine, nigrosine salt, Nigrosine compounds such as nigrosine derivatives; acid dyes composed of nigrosine compounds such as nigrosine BK, nigrosine NB, nigrosine Z; metal salts of naphthenic acid or higher fatty acids; alkoxylated amines; alkylamides; benzylmethylhexyldecylammonium chloride, decyltrimethylammonium chloride And quaternary ammonium salts such as These may be used alone or in combination of two or more. In particular, the nigrosine compound is optimal for use as a positively chargeable toner from the viewpoint of obtaining a quicker start-up property.

  Further, a quaternary ammonium salt, a carboxylate, or a resin or oligomer having a carboxyl group as a functional group can also be used as a positively chargeable charge control agent. Specifically, a styrene resin having a quaternary ammonium salt, an acrylic resin having a quaternary ammonium salt, a styrene-acrylic resin having a quaternary ammonium salt, a polyester resin having a quaternary ammonium salt, and a carboxylate Styrene resin having carboxylate, acrylic resin having carboxylate, styrene-acrylic resin having carboxylate, polyester resin having carboxylate, polystyrene resin having carboxyl group, acrylic resin having carboxyl group 1 type, or 2 or more types, such as a styrene-acrylic resin having a carboxyl group and a polyester resin having a carboxyl group.

  As the charge control agent exhibiting negative chargeability, for example, organometallic complexes and chelate compounds are effective. Specific examples include aluminum acetylacetonate, iron (II) acetylacetonate, chromium 3,5-di-tert-butylsalicylate, etc., and acetylacetone metal complexes, salicylic acid metal complexes or salts are preferred, and salicylic acid compounds are particularly preferred. Metal complexes or salicylic acid metal salts are preferred.

  The above-described positively or negatively chargeable charge control agent is 1.5 to 15 parts by weight, preferably 1.5 to 8.0 parts by weight, and more preferably 1.5 to 100 parts by weight of the binder resin. It is preferable to be contained in the toner at a ratio of ˜7.0 parts by weight. If the addition amount of the charge control agent is smaller than the above range, it tends to be difficult to stably charge the toner to a predetermined polarity, and the electrostatic latent image is developed using this toner to develop an image. When forming, the image density tends to decrease or the durability of the image density tends to decrease. In addition, the charge control agent tends to be poorly dispersed, causing so-called fogging, and the contamination of the photoconductor tends to be severe. On the other hand, when the charge control agent is used in a larger amount than the above range, it tends to cause defects such as environmental resistance, particularly poor charging under high temperature and high humidity and defective images, and contamination of the photoreceptor.

  In addition, when the binder resin is allowed to have a part of the charge control action without using a charge control agent, a copolymer having an anionic or cationic polar group as a part of the binder resin. Use coalescence. Cationic polar groups include basic nitrogen-containing groups such as primary, secondary or tertiary amino groups, quaternary ammonium groups, amide groups, imino groups, imide groups, hydrazino groups, guanidino groups, amidino groups, etc. However, examples of the anionic polar group include polar groups such as carboxylic acid, sulfonic acid, and phosphonic acid. Examples of the resin include resins obtained by polymerizing cationic or anionic polar group-containing monomers with other monomers or resins by means of random copolymerization, block copolymerization, graft copolymerization, or the like.

(wax)
The wax used for improving the fixing property and the offset resistance is not particularly limited. For example, polyethylene wax, polypropylene wax, Teflon (registered trademark) wax, Fischer-Tropsch wax, paraffin wax, It is preferable to use ester wax, montan wax, rice wax or the like. Two or more of these waxes may be used in combination. By adding such wax, offset property and image smearing (dirt around the image when the image is rubbed) can be more efficiently prevented.

  The wax is preferably blended at a ratio of 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. If the added amount of the wax is less than 1 part by weight, offset properties and image smearing tend not to be effectively prevented. On the other hand, if the added amount exceeds 10 parts by weight, the toners are fused and stored. The stability tends to decrease.

  The toner can be produced by a method known per se such as a pulverization classification method, a melt granulation method, a spray granulation method, a polymerization method, etc., but the pulverization classification method is general. In the pulverization classification method, each toner component is premixed with a mixer such as a Henschel mixer, and then kneaded using a kneading apparatus such as a twin screw extruder. The kneaded composition is cooled, pulverized and classified. Use toner particles.

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

(External additive)
Examples of the external additive include inorganic metal oxides. Examples of the inorganic metal oxides include titanium oxide, alumina, magnesium oxide, zinc oxide, strontium titanate, and barium titanate. By treating the surface of the toner particles with these external additives, fluidity, storage stability, cleaning properties, and the like can be improved.

  In addition to the above inorganic metal oxide, externally added 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). You can also. These external additives are usually used at a ratio of 0.2 to 10.0 parts by weight with respect to 100 parts by weight of the toner. Furthermore, in order to reduce the frictional resistance with the photoreceptor, for example, zinc stearate or the like may be added at a ratio of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the toner.

<Carrier>
As the carrier, either a nonmagnetic carrier or a magnetic carrier can be used. Examples of nonmagnetic carriers include glass particles and resin carriers. Examples of the magnetic carrier include magnetic particles and so-called coating carriers obtained by coating magnetic particles with a resin.

  The volume average particle diameter of the carrier is preferably about 20 to 100 μm. The average particle size of the carrier can be measured using a laser diffraction / scattering particle size measuring device, and examples of the measuring device include LA-700 manufactured by Horiba, Ltd.

  Examples of the magnetic particles include magnetic metals such as iron, nickel, cobalt, and alloys thereof, alloys containing rare earths, hematite, magnetite, manganese-zinc ferrite, nickel-zinc ferrite, manganese -Soft ferrites such as magnesium ferrite and lithium ferrite, iron oxides such as copper-zinc ferrite, and mixtures thereof.

  Examples of the resin for coating magnetic particles include silicone resins such as methyl silicone and methyl phenyl silicone; fluorine resins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, monochlorotrifluoroethylene, monochloroethylene, and trifluoroethylene. Resins; (Meth) acrylic resins such as methyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate; Styrene resins such as styrene, chlorostyrene, and methylstyrene; Styrene-acrylic resins; Polyester resins; Examples thereof include polyamide-based resins, and these may be used alone or in combination. Among these resins, silicone resins and fluorine resins are desirable from the viewpoint of durability and spent resistance.

  The non-magnetic one-component developer is composed only of the toner. A magnetic one-component developer is one in which the toner particles contain a magnetic substance. As the magnetic material, a magnetic material used for the magnetic carrier can be used.

  The two-component developer is a mixture of the above-described fine particles and toner in a carrier. The mixture of fine particles and toner is usually mixed in a ratio of 3 to 10 parts by weight with respect to 100 parts by weight of the carrier.

  As described above, the present invention can also be applied to a wet developer. The wet developer has a configuration in which toner is dispersed in an electrically insulating liquid. As the electrically insulating liquid, a hydrocarbon solvent or the like is used. As the toner, toner having substantially the same structure as that in the dry developer can be used.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In this example, the glass transition temperature (Tg), melting point (Tm) of the resin, the volume average particle diameter and coefficient of variation (CV) in the number distribution of the toner, and the volume average particle diameter of the carrier are as follows. Measured.

(Glass-transition temperature)
Using a differential scanning calorimeter (DSC), it was determined from the change point of specific heat. Specifically, an endothermic curve was measured using a differential scanning calorimeter “DSC-6200” manufactured by Seiko Instruments Inc. as a measuring device. For the endothermic curve, 10 mg of a measurement sample is put in an aluminum pan, and an empty aluminum pan is used as a reference. Got in. And the glass transition temperature was calculated | required from the obtained endothermic curve.

(Melting point)
The peak of the endothermic peak was determined as the melting point using DSC. The measuring method is the same as the DSC measuring method.

(Volume average particle diameter of toner)
Measurement was performed using Multisizer 3 (Beckman Coulter, Inc.).

(Coefficient of variation)
The multisizer 3 outputs the measurement result of the coefficient of variation together with the volume average particle diameter of the toner.

(Volume average particle diameter of carrier)
It measured using the laser diffraction scattering type particle diameter measuring apparatus (LA-700 by Horiba, Ltd.).

<Manufacture of fine particles A>
First, 100 parts by weight of a polyester resin (Sekisui Chemical Co., Ltd., Tg1 = 55 ° C., Tm1 = 125 ° C.), 4 parts by weight of carbon black (PRINTEX90, manufactured by Degussa), charge control agent (FCA201PS, Fujikura Kasei) 4 parts by weight were premixed, melt-kneaded and extruded to form a resin plate having a thickness of 10 μm. Subsequently, the resin plate was punched out with a mold in which letters were engraved in a convex shape to obtain substantially cubic fine particles A having a size of 8 μm × 8 μm (thickness 10 μm). On the surface of the fine particles A, 8 letters having a size of about 1 μm × 1 μm are imprinted in a concave shape.

<Manufacture of black toner>
A polyester resin (manufactured by Sekisui Chemical Co., Ltd., Tg2 = 52 ° C., Tm2 = 122 ° C.) is used as a binder resin, and 100 parts by weight of this binder resin is 5 parts by weight of carbon black (PRINTEX 90, manufactured by Degussa). 4 parts by weight of charge control agent (FCA201PS, manufactured by Fujikura Kasei Co., Ltd.) and 5 parts by weight of wax (Sun Wax LEL-250, manufactured by Sanyo Kasei Kogyo Co., Ltd.) are premixed and then melt-kneaded, coarsely pulverized, and finely pulverized. Then, a black toner having a volume average particle size of 7.0 μm and a coefficient of variation (CV, Coefficient of Variation) in the number distribution of 25% was obtained.

<Production of two-component developer A>
First, a mixture obtained by adding 5 parts by weight of the fine particles A to 100 parts by weight of the obtained black toner was put into a Henschel mixer (FM-10C type, manufactured by Mitsui Mining Co., Ltd.), and 2 at 20 ° C. and 2000 rpm. Stir for minutes. Subsequently, 6 parts by weight of the obtained mixture was added to 100 parts by weight of a magnetic carrier (Fe ferrite coated with polyester resin, volume average particle diameter 45 μm) to obtain a two-component developer A.

<Confirmation of fine particles A in printed matter>
The obtained two-component developer A is set in an electrophotographic apparatus (color multifunction machine KM-C3232, manufactured by Kyocera Document Solutions Co., Ltd.), printed out, and an image portion of the obtained printed matter is observed with an optical microscope (magnification 20). Times). As a result, fine particles A in which characters were engraved were confirmed. When the printed matter was observed with the naked eye, there was no problem as a printed matter.

Claims (3)

A developer containing at least a toner used in an electrophotographic apparatus, containing fine particles mainly containing a resin in addition to the toner, and an identification mark formed on the fine particles,
The toner contains a binder resin, and the glass transition temperature Tg1 (° C.) of the resin, which is the main component of the fine particles, and the glass transition temperature Tg2 (° C.) of the binder resin in the toner are Tg2 <Tg1. <Developer characterized by having a relationship of (Tg2 + 10). A developer containing at least a toner used in an electrophotographic apparatus, containing fine particles mainly containing a resin in addition to the toner, and an identification mark formed on the fine particles,
The toner contains a binder resin, and the melting point Tm1 (° C.) of the resin, which is the main component of the fine particles, and the melting point Tm2 (° C.) of the binder resin in the toner are Tm2 <Tm1 <(Tm2 + 10). A developer characterized by having the following relationship:   The developer according to claim 1, wherein 0.1 to 15 parts by weight of the fine particles are contained with respect to 100 parts by weight of toner.