JP4010214B2 - Carrier for electrostatic image developer, electrostatic image developer - Google Patents

Description

【００９９】
【表２】

【０１００】
【表３】

【０１０１】
【発明の効果】
以上、本発明によれば、磁性体からなる芯材に少なくとも表面を樹脂で被覆したキャリアにおいて該キャリアの被覆樹脂中に樹脂粒子又は導電性粒子が少なくとも１種類以上が分散含有されてなり該樹脂粒子又は該導電性粒子の少なくとも１種類以上がワックスで表面を被覆してあることを特徴とする静電荷像現像剤用キャリア及び該キャリアを使用した現像剤は帯電性、転写性、クリーニング性が優れ、安定した画質維持性を実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrostatic charge image developing carrier and an electrostatic charge image developer used in electrophotography, electrostatic recording method and the like.
[0002]
[Prior art]
An electrophotographic method for visualizing image information through an electrostatic latent image is currently used in various fields and is known (see Patent Documents 1 and 2). In the electrophotographic method, generally, an electrostatic latent image is formed on a photoreceptor in a charging / exposure process, and the electrostatic latent image is developed with a developer containing toner in a developing process to form a toner image. In the transfer step, the toner image is transferred onto a transfer material such as paper or sheet. In the fixing step, the toner image is fixed on the transfer material using heat, solvent, pressure, etc. How to get.
There are many known developing methods for the developer. In addition to the cascade development method (see Patent Document 3), magnetic brush method (see Patent Document 4), and touchdown method (see Patent Document 5), development is performed by applying a bias electric field between the developer carrying member and the photosensitive member. There is a jumping brush development method.
[0003]
Among them, a typical method of so-called two-component developer obtained by mixing a carrier and a toner is a magnetic brush method. In this method, magnetic particles such as steel and ferrite are used as a carrier, a developer composed of toner and a magnetic carrier is supported by a magnet, and the developer is formed in a brush shape by the magnetic field of the magnet. Next, when the magnetic brush comes into contact with the electrostatic latent image on the photoreceptor, the toner in the brush is attracted according to the amount of charge of the latent image and developed. The carrier is roughly classified into a coated carrier having a coating on the surface and an uncoated carrier having no coating on the surface, but the coated carrier is superior when considering the lifetime of the developer. Therefore, various coated carriers have been developed and put into practical use. The properties of the coated carrier are required to at least be able to impart appropriate chargeability (charge amount and charge distribution) to the toner and to maintain the appropriate chargeability over a long period of time. Therefore, various coated carriers have been proposed that do not change the chargeability of the toner, are excellent in impact resistance and friction resistance, and are stable against environmental changes such as humidity and temperature.
[0004]
  For example, nitrogen-containing fluorinated alkyl (meth) axReBy coating the surface of the carrier core with a copolymer of a rate and a vinyl monomer or a copolymer of a fluorinated alkyl (meth) acrylate and a nitrogen-containing vinyl monomer, a coated carrier having a relatively long life is obtained. (See Patent Documents 6 to 8). Further, it is described that a polyamide resin or a melamine resin is respectively coated on the surface of a carrier core material and cured to obtain a coated carrier having a relatively hard coating (see Patent Documents 9 to 10).
[0005]
However, in the case of these carriers, there is a problem that contamination (impact) on the carrier surface by the toner component cannot be prevented. In order to prevent the impaction, for example, it is considered to form a carrier film using a resin having a small surface energy such as a silicone resin or a fluorine resin (see Patent Documents 11 to 12). . However, in such a carrier, although the silicone resin and the fluorine-based resin exist relatively in the vicinity of the carrier surface, there are only a few in the thickness direction of the coating layer. When used over a period of time, the effect of the resin is gradually lost due to wear of the coating, and conversely, the impact occurs. In addition, when continuous copying is performed using such a developer, an image having excellent density reproducibility and image quality can be initially obtained. However, after copying tens of thousands of sheets, the image density decreases and The tonality and graininess become poor. In other words, image quality deterioration due to contamination (impact) on the carrier surface was inevitable.
[0006]
Moreover, in order to obtain durability while controlling the electrical resistance as a carrier low, a coated carrier using a wax together with a thermosetting resin has been proposed (see Patent Documents 13 to 14). However, in these cases, since the carrier surface or the coating layer is not uniformly dispersed in the thickness direction, the impact prevention effect is not sufficiently obtained, and the coating can be temporarily suppressed but the coating layer disappears over time. The effect disappeared.
[0007]
[Patent Document 1]
US Pat. No. 2,297,691,
[Patent Document 2]
U.S. Pat. No. 2,357,809
[Patent Document 3]
U.S. Pat. No. 2,618,552
[Patent Document 4]
U.S. Pat. No. 2,874,063
[Patent Document 5]
U.S. Pat. No. 2,895,847
[Patent Document 6]
JP 61-80161 A
[Patent Document 7]
JP 61-80162 A
[Patent Document 8]
JP 61-80163 A
[Patent Document 9]
Japanese Patent Laid-Open No. 1-18150
[Patent Document 10]
Japanese Patent Laid-Open No. 2-79862
[Patent Document 11]
JP-A-60-186844
[Patent Document 12]
JP-A 64-13560
[Patent Document 13]
JP-A-8-44118
[Patent Document 14]
JP-A-9-288384
[0008]
[Problems to be solved by the invention]
An object of the present invention is to solve the conventional problems and achieve the following objects. That is, an object of the present invention is to provide an electrostatic charge image developing carrier and an electrostatic charge image developer aimed at solving the above problems.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors can achieve the above object by using one or more kinds of resin fine particles and / or conductive particles having a wax coating on a carrier. I found. Specifically:
[0010]
  (1) In a carrier in which the surface of a core made of a magnetic material is coated with a resin, one or more kinds of particles selected from resin particles or conductive particles are dispersed and contained in the resin, and the particles are dispersed and contained One kind ofThe surface of is coated with alkoxysilane, an organosilane compound formed from alkoxysilane, or polysiloxane, and the wax component is attached to the coating.A carrier for an electrostatic charge image developer.
[0011]
(2) The electrostatic image developer carrier according to (1), wherein the particles whose surfaces are coated with wax are conductive particles.
[0012]
(3) The electrostatic charge image developer of (1) or (2) above, wherein the surface of the particles coated with wax is coated with a wax component to a thickness of 0.5 to 5 nm. For carrier.
[0013]
  (4) 0.1 to 45 parts by weight of the alkoxysilane or polysiloxane is added to 100 parts by weight of the resin particles or conductive particles, and the production of (1) to (3) The carrier for an electrostatic charge image developer according to any one of the items.
[0014]
(5) The electrostatic charge image developer according to any one of (1) to (4), wherein the particles dispersedly contained in the coating resin of the carrier are resin particles made of a nitrogen-containing resin. For carrier.
[0015]
(6) Any of (1) to (4), wherein the particles dispersed and contained in the coating resin of the carrier are carbon black, a metal, a simple substance of a metal oxide, or a composite thereof. 2. The carrier for an electrostatic charge image developer according to item 1.
[0016]
  (7) In an electrostatic charge image developer composed of a carrier and a toner, the toner has a shape factor SF1 (ML²/ A) is a toner in the range of 100 to 140, the carrier has a coating resin on the surface of the core material made of a magnetic material, and the resin coating contains 1 particle selected from resin particles or conductive particles. One kind of particles that are dispersed and contained in more than one kind.The surface of is coated with alkoxysilane, an organosilane compound formed from alkoxysilane, or polysiloxane, and the wax component is attached to the coating.An electrostatic charge image developer which is a carrier.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
  The carrier in the present invention will be described.
  In the carrier of the present invention, at least one kind of particles selected from resin particles or conductive particles is dispersedly contained in the coating resin, and at least one kind of the particles contained in the dispersion is contained.The surface of is coated with alkoxysilane, an organosilane compound formed from alkoxysilane, or polysiloxane, and the wax component is attached to the coating.It is necessary.
[0018]
In a developer composed of a toner and a carrier, the chargeability of the developer deteriorates (decreases) with long-term use. As a result, there arises a problem that internal contamination and fogging on the transfer material occur. One of the causes is that the carrier surface is contaminated with a toner component containing a toner surface additive by long-term use. The details are not clear, but the mechanism is roughly classified. 1) The charge imparting ability is lowered by switching the contaminated carrier part from the carrier surface component to the contaminated component (impact-dominated type). 2) The carrier coating layer is worn or broken due to the developer agitating stress or collision between carriers in the developer (coating layer degradation type). Further, as another adverse effect due to wear and breakage, the core surface is exposed to reduce carrier resistance, and image quality defects due to carrier scattering resulting from carrier resistance reduction occur.
[0019]
With respect to the above problems, the impact can be suppressed to some extent by using a low surface energy material typified by a fluororesin or a silicone resin for the coating layer. Further, even if the resin resin particles having the charge imparting property are added to reduce the coating resin layer, the resin particles are always present on the carrier surface, so that a desired charge amount can be obtained even by long-term use. In addition, by using conductive particles, a desired resistance can be suppressed because a constant conductivity is always exhibited even when the resistance is increased due to impaction, or conversely, the resistance is decreased due to wear of the coating layer.
[0020]
However, when the toner is used for a longer period, the toner component starts to impact on the resin particles and conductive particles. Therefore, the impact can be suppressed by surface-treating the resin particles and the conductive particles. Examples of the surface treatment agent include known materials such as silane coupling agents, titanate-based, aluminum-based coupling agents, or silicone oil treatment. However, these treatment agents are limited in uniformity, throughput, and treatment layer thickness.
[0021]
  Therefore, as a result of intensive studies by the present inventors, the surface of the particles wasCoating with alkoxysilane, organosilane compound produced from alkoxysilane or polysiloxane, and attaching wax component to the coatingIt was found that the effect can be obtained. This wax is preferably coated uniformly with a thickness of 0.5 to 50 nm.
[0022]
The resin particles of the present invention are in the range of 5 to 40% by weight, more preferably 10 to 30% by weight, based on the amount of the carrier coating resin. When the amount is less than 5% by weight, there is no charge maintaining effect, and when the amount exceeds 40% by weight, the coating layer becomes brittle, and the coating layer breaks down easily after long-term use. Moreover, electroconductive particle is 5 to 60 weight%, More preferably, it is 10 to 40 weight%. If it is 5 parts by weight or less, the desired conductivity may not be obtained. On the other hand, when the amount is more than 60% by weight, the carrier resistance is remarkably lowered, and an image quality defect derived from low resistance may occur.
[0023]
  The present invention is described in detail below.
  The manufacturing method of the resin particle which coat | covered the surface with the wax which concerns on this invention, and electroconductive particle is described. The resin particles or conductive particles whose surfaces are coated with the wax according to the present invention are, for example, a mixture of resin particles or conductive particles and alkoxysilane or polysiloxane, and the particle surface of the resin particles or conductive particles is alkoxysilane., Organosilane compounds formed from alkoxysilanesOr coated with polysiloxane and then alkoxysilane, Organosilane compoundsAlternatively, it can be obtained by mixing resin particles or conductive particles coated with polysiloxane and wax.
[0024]
  Resin particle or conductive particle alkoxysilane, Organosilane compounds formed from alkoxysilanesOr, coating with polysiloxane can be mechanically mixed and stirred with resin particles or conductive particles and alkoxysilane or polysiloxane, or mechanically mixed and stirred while spraying alkoxysilane or polysiloxane on resin particles or conductive particles. do it. Almost all of the added alkoxysilane or polysiloxane is coated on the surface of resin particles or conductive particles. In addition, the coated alkoxysilane may be coated as an organosilane compound produced from alkoxysilane, a part of which is produced through a coating process. Even in this case, there is no influence on the subsequent adhesion of the wax.
[0025]
  Mixing and stirring resin particles or conductive particles and alkoxysilane or polysiloxane, and the wax and particle surfaceAlkoxysilane,As an apparatus for mixing and stirring with resin particles or conductive particles coated with an organosilane compound or polysiloxane, an apparatus capable of applying a shearing force to the powder layer is preferable. A device capable of simultaneously performing compression and compression, for example, a wheel-type kneader, a ball-type kneader, a blade-type kneader, or a roll-type kneader can be used. In carrying out the present invention, a wheel-type kneader can be used more effectively. Specific examples of the wheel type kneader include edge runners (synonymous with “mix muller”, “simpson mill”, “sand mill”), multi-mal, stotz mill, wet pan mill, conner mill, ring muller, and the like. , Preferably an edge runner, multi-mal, Stots mill, wet pan mill, and ring muller, and more preferably an edge runner. Specific examples of the ball kneader include a vibration mill. Specific examples of the blade-type kneader include a Henschel mixer, a planetary mixer, and a nauta mixer. Specific examples of the roll-type kneader include an extruder.
[0026]
The conditions at the time of mixing and stirring are such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm) so that the surface of the resin particles or the conductive particles is coated with alkoxysilane or polysiloxane as uniformly as possible. The treatment conditions are preferably 98 to 1470 N / cm (10 to 150 Kg / cm), more preferably 147 to 980 N / cm (15 to 100 Kg / cm), and the treatment time is 5 to 120 minutes, preferably 10 to 90 minutes. May be adjusted as appropriate. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.
[0027]
As for the addition amount of alkoxysilane or polysiloxane, 0.15-45 weight part is preferable with respect to 100 weight part of resin particles or electroconductive particle. When the amount is less than 0.15 parts by weight, it is difficult to attach a wax that can obtain resin particles or conductive particles whose surfaces are uniformly coated with the target wax. With the addition amount of 0.15 to 45 parts by weight, 3 to 30 parts by weight of wax can be attached to 100 parts by weight of the resin particles, so there is no point in adding more than necessary beyond 45 parts by weight.
[0028]
  Then alkoxysilane, Organosilane compoundsAlternatively, add wax to resin particles or conductive particles coated with polysiloxane, mix and stir, and coat with alkoxysilane, Organosilane compound coatingAlternatively, wax is applied to the polysiloxane coating. If necessary, drying or heat treatment may be further performed.
[0029]
The wax is preferably added in small portions over time, particularly over about 5 to 60 minutes.
[0030]
The condition during mixing and stirring is such that the linear load is 19.6 to 1960 N / cm (2 to 200 Kg / cm), preferably 98 to 1470 N / cm (10 to 150 Kg / cm), so that the wax uniformly adheres. The treatment conditions may be adjusted as appropriate, preferably in the range of 147 to 980 N / cm (15 to 100 Kg / cm) and the treatment time of 5 to 120 minutes, preferably 10 to 90 minutes. In addition, what is necessary is just to adjust process conditions suitably in the range of stirring speed 2-2000rpm, Preferably 5-1000rpm, More preferably, it is 10-800rpm.
[0031]
The addition amount of the wax is 0.15 to 30 parts by weight with respect to 100 parts by weight of the resin particles. Preferably it is 0.15-15 weight part. When the addition amount of the wax is outside the above range, resin particles or conductive particles whose surface is uniformly coated with the target wax cannot be obtained.
[0032]
The heating temperature in the drying or heating step is usually preferably 40 to 150 ° C, more preferably 60 to 120 ° C. The treatment time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours.
[0033]
  The alkoxysilane used for coating the resin particles is finally coated with an organosilane compound generated from the alkoxysilane through these steps.May.
[0034]
Examples of the resin particles used in the present invention include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins are preferable from the viewpoint of relatively easily increasing the hardness, and resin particles made of nitrogen-containing resin containing N atoms are preferable from the viewpoint of imparting negative chargeability to the toner. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together.
[0035]
As an average particle diameter of the said resin particle, about 0.1-2 micrometers is preferable, for example, More preferably, it is 0.2-1 micrometer. When the average particle size of the resin particles is less than 0.1 μm, the dispersibility of the resin particles in the coating is very poor. On the other hand, when the average particle size exceeds 2 μm, the resin particles easily fall off from the coating, and the original effect is obtained. It may stop working.
[0036]
Examples of the conductive particles of the present invention include carbon black, metals, metal oxide simple substances, or composites thereof. Specifically, for example, carbon black particles, metal particles such as gold, silver, and copper, Examples include conductive oxide particles such as titanium oxide and zinc oxide, particles with titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder and the like covered with tin oxide, carbon black, metal, etc. It is done.
[0037]
These may be used individually by 1 type and may use 2 or more types together. Among these, carbon black particles are preferable from the viewpoints of production stability, cost, conductivity, and the like. The type of carbon black is not particularly limited, but carbon black having a DBP oil absorption of about 50 to 250 ml / 100 g is preferable because of excellent production stability.
[0038]
The wax for coating the resin particles or conductive particles in the present invention is not particularly limited, and examples thereof include paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, Polyolefin wax and derivatives thereof. Derivatives include oxides, polymers with vinyl monomers, and graft modified products. In addition, alcohols, fatty acids, plant waxes, animal waxes, mineral waxes, ester waxes, acid amides, and the like can be used. Other known materials can also be used. The melting point of the wax is preferably 60 degrees or more. More preferably, it is 80 degrees or more. If it is less than 60 degree | times, the fluidity | liquidity as a carrier will deteriorate.
[0039]
Examples of the carrier core material in the present invention include magnetic metals such as iron, steel, nickel, cobalt, alloys of these with manganese, chromium, rare earth, and magnetic oxides such as ferrite and magnetite. From the viewpoint of core material surface properties and core material resistance, ferrite, particularly alloys with manganese, lithium, strontium, magnesium and the like are preferable, but not limited thereto. The average particle diameter of the core is generally 10 to 500 μm, preferably 30 to 100 μm.
[0040]
The carrier in the present invention is obtained by coating a resin on the surface of the core material, and the resin is not particularly limited as long as it can be used as a matrix resin, and can be appropriately selected according to the purpose. Polyolefin resins such as polyethylene and polypropylene; polyvinyl resins and polyvinylidene resins such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone; Vinyl chloride-vinyl acetate copolymer; Styrene-acrylic acid copolymer: Straight silicone resin composed of organosiloxane bonds or modified products thereof; polytetrafluoroethylene, polyvinyl fluoride, polyfluoride Fluorine resins such as nilidene and polychlorotrifluoroethylene; silicone resins: polyesters; polyurethanes; polycarbonates; phenol resins; urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and other amino resins; epoxy resins, etc. These are known resins per se. These may be used individually by 1 type and may use 2 or more types together. In the present invention, among these resins, it is preferable to use at least a fluorine resin and / or a silicone resin. The use of at least a fluorine-based resin and / or a silicone resin as the resin is advantageous in that it has a high effect of preventing carrier contamination (impact) due to toner and external additives.
[0041]
  Specifically, the carrier core material isRecordFilm formation, dipping method in which the film forming liquid is immersed, spray method in which the film forming liquid is sprayed on the surface of the carrier core material, and the film forming liquid in a state where the carrier core material is suspended by flowing air And kneader coater method for removing the solvent. Among these, the kneader coater method is preferable in the present invention.
[0042]
The solvent used in the film-forming liquid is not particularly limited as long as it can dissolve only the resin as a matrix resin, and can be selected from among solvents known per se, for example, And aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and ethers such as tetrahydrofuran and dioxane.
[0043]
When the resin particles are dispersed in the coating, since the resin particles and the particles as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface, the carrier is used for a long time. Even when the coating is worn, the same surface formation as when not in use can always be maintained, and a good charge imparting ability for the toner can be maintained over a long period of time. In the case where the conductive particles are dispersed in the resin, the conductive particles and the resin as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface. Even if the coating is worn out over a long period of time, the same surface formation as when not in use can be maintained, and carrier deterioration can be prevented for a long time. In the case where the resin particles and the conductive particles are dispersed in the coating, the above-described effects can be achieved at the same time.
[0044]
The average film thickness of the resin coating layer is usually 0.1 to 10 μm, but in the present invention, it is preferably in the range of 0.5 to 3 μm in order to develop a stable volume resistivity of the carrier over time. .
[0045]
The volume resistivity of the carrier formed as described above corresponds to the upper and lower limits of a normal development contrast potential in order to achieve high image quality.^Three-10^FourIn the range of V / cm, 10⁶-10¹⁴It is preferably Ωcm. The volume resistivity of the carrier is 10⁶If it is less than Ωcm, the reproducibility of fine lines is poor, and toner fogging on the background due to charge injection tends to occur. The volume resistivity of the carrier is 10¹⁴If it is larger than Ωcm, black solid and halftone reproduction will be worse. In addition, the amount of carrier transferred to the photoconductor increases and the photoconductor is easily damaged.
[0046]
The two-component developer of the present invention is effective when combined with the specific carrier described above and the specific toner described below.
[0047]
The toner for developing an electrostatic latent image is composed of a binder resin, a colorant, and a release agent, and a toner having a volume average particle diameter of 2 to 8 μm can be used. Toner average shape index SF1 (ML²/ A) 100 to 140 can be used to obtain images with high development, transferability and high image quality.
[0048]
The toner used in the present invention is not particularly limited by the production method as long as it satisfies the above shape index and particle size, and a known method can be used.
[0049]
For example, the toner is produced by kneading, pulverizing, and classifying a binder resin, a colorant, a release agent, and, if necessary, a charge control agent. Method of changing shape by force or thermal energy, emulsion polymerization of polymerizable monomer of binder resin, dispersion of formed dispersion, colorant, release agent, and charge control agent as required Emulsion polymerization agglomeration method to obtain toner particles by mixing and agglomerating and heat fusing the liquid, polymerizable monomer and colorant, release agent, and charge control agent if necessary Suspension polymerization method in which the solution is suspended in an aqueous solvent for polymerization, a binder resin and a colorant, a release agent, and if necessary, a solution such as a charge control agent is suspended in an aqueous solvent for granulation A suspension method or the like can be used. In addition, a manufacturing method may be performed in which the toner obtained by the above method is used as a core, and agglomerated particles are further adhered and heat-fused to give a core-shell structure. In particular, a wet-process toner that makes it easy to obtain a spherical toner is preferably used, and toner particles obtained by an emulsion polymerization aggregation method are preferably used from the viewpoint that toner particles having a sharp distribution can be obtained.
[0050]
As the binder resin used, styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate, Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Homopolymers and copolymers such as vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone. In particular, typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-anhydride maleate. Examples thereof include acid copolymers, polyethylene, and polypropylene. Further examples include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like.
[0051]
In addition, toner colorants include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, and malachite green oxa. Rate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 can be exemplified as a representative one.
[0052]
Typical examples of the releasing agent include low molecular weight polyethylene, low molecular weight polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax, and candelilla wax.
[0053]
In addition, a charge control agent may be added to the electrostatic latent image developing toner of the present invention as necessary. Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, and resin type charge control agents containing polar groups can be used. When the toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. The toner in the present invention may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.
[0054]
Examples of inorganic oxide fine particles added to the toner include SiO.₂, TiO₂, Al₂O_Three, CuO, ZnO, SnO₂, CeO₂, Fe₂O_Three, MgO, BaO, CaO, K₂O, Na₂O, ZrO₂, CaO · SiO₂, K₂O. (TiO₂) N, Al₂O_Three・ 2SiO₂, CaCO_Three, MgCO_Three, BaSO_Four, MgSO_FourEtc. can be illustrated. Of these, silica fine particles and titania fine particles are particularly preferable. It is desirable that the surface of the oxide fine particles is previously hydrophobized. This hydrophobization treatment is more effective for improving the powder fluidity of the toner, as well as the environmental dependency of charging and the resistance to carrier contamination.
[0055]
The hydrophobizing treatment can be performed by immersing the inorganic oxide in a hydrophobizing agent. Although there is no restriction | limiting in particular as said hydrophobic treatment agent, For example, a silane coupling agent, a silicone oil, a titanate coupling agent, an aluminum coupling agent etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Of these, silane coupling agents are preferred.
[0056]
As the silane coupling agent, for example, any one of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltriethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N- (trimethylsilyl) ) Urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysila , Γ-methacryloxypyrrolyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyl Examples include trimethoxysilane and γ-chloropropyltrimethoxysilane.
[0057]
The amount of the hydrophobizing agent varies depending on the kind of the inorganic oxide fine particles and cannot be generally defined, but is usually about 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic oxide fine particles.
[0058]
The electrostatic charge image developer of the present invention is desirably used in the range of 2 to 15 parts by weight of toner with respect to 100 parts by weight of carrier.
[0059]
【Example】
  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following explanation,SpecialUnless otherwise specified, “parts” means “parts by weight”.
[0060]
The measurement method used in the present invention will be described below.
<Measurement of coating uniformity of inorganic oxide fine powder>
(1) Disperse sample particles in a two-component mixed epoxy solution and let it stand for one day to solidify.
(2) Then, a section having a thickness of 100 nm is prepared with a microtome.
(3) The section is placed on a copper mesh, set in a high-resolution electron microscope JEM-2010 (manufactured by JEOL Ltd.), and photographed at 500,000 times with an applied voltage of 200 kV.
(4) Pull the negative 3 times to 10 times and print.
(5) The surface of the particle having a cross section of 10 particles is arbitrarily observed by printing according to the procedures of (1) to (4), and the surface coating state on the entire surface of the particle is evaluated. Coverage ratio = coating length / particle total surface length × 100 (%)
[0061]
<Toner shape SF1 (ML²/ A)>
In the present invention, the average shape index SF1 (ML²/ A) means the value calculated by the following formula.²/ A = 100.
ML²/ A = (maximum length) 2 × π × 100 / (area × 4)
As a specific method for obtaining the average shape index, a toner image is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco Corp.), the equivalent circle diameter is measured, and the maximum length and area are individually measured. ML of the above formula for the particles of²Find the value of / A.
[0062]
<Charge amount measurement>
The charge amount in the actual machine evaluation test was measured with a TB200 manufactured by Toshiba under the conditions of a measurement environment of 25 ° C. and 55% RH by collecting the developer on the mag sleeve in the developing device.
[0063]
<Solid Area Density>
The image density was measured using X-Rite 938A (X-Rite).
[0064]
<Image quality>
Regarding the initial image quality, a chart having a density gradation was copied, and the gradation, density uniformity, and presence / absence of an edge effect were visually evaluated. The image quality after copying 100,000 sheets was evaluated in terms of graininess, gradation / pseudo contour, density reproducibility, and other image quality defects.
[0065]
-Preparation of wax-coated resin fine powder A-
3,000 parts by weight of phenol resin particles (average particle size 0.5 μm, toluene insoluble) were introduced into Edge Runner “MPUV-2 type” (product name, manufactured by Matsumoto Foundry Co., Ltd.), and methyltriethoxysilane (trade name: TSL8123: manufactured by Toshiba Silicone Co., Ltd.) A methyltriethoxysilane solution obtained by mixing and diluting 30 parts by weight with 200 parts by weight of ethanol was added to the phenol resin particles while the edge runner was operated, and mixed and stirred. .
[0066]
Next, 60 parts by weight of refined granular carnauba wax (melting point: 82 degrees, manufactured by Toa Kasei Co., Ltd.) is added over 10 minutes while operating the edge runner, and the mixture is stirred, over the methyltriethoxysilane coating. After depositing carnauba wax, heat treatment was performed at 105 ° C. for 60 minutes using drying to obtain wax-coated resin fine powder A.
The average particle size was 0.5 μm, and the coating state was observed. As a result, the coating thickness was in the range of 2.0 to 5.0 nm, and 100% of the fine powder surface was coated.
[0067]
-Adjustment of wax-coated resin fine powder B-
3000 parts by weight of cross-linked melamine resin particles (average particle size 0.3 μm, toluene insoluble) were introduced into edge runner “MPUV-2” (product name, manufactured by Matsumoto Casting Iron Works Co., Ltd.) and methyltriethoxysilane (trade name) : TSL8123: manufactured by Toshiba Silicone Co., Ltd.) A methyltriethoxysilane solution obtained by mixing and diluting 30 parts by weight with 200 parts by weight of ethanol is added to the crosslinked melamine resin particles while the edge runner is operated, and mixed and stirred. went.
[0068]
Next, 40 parts by weight of polywax 725 powder (melting point: 103 ° C., manufactured by Toyo Petrolite Co., Ltd.) is added over 10 minutes while operating the edge runner, and mixed and stirred. After the polywax 725 was adhered to the substrate, heat treatment was performed at 105 ° C. for 60 minutes using drying to obtain a wax-coated resin fine powder B.
The average particle size was 0.3 μm, and the coating state was observed. As a result, the coating thickness was in the range of 1.0 to 2.0 nm, and 100% of the fine powder surface was coated.
[0069]
-Preparation of wax-coated inorganic oxide fine powder C-
Carbon black (average primary particle size 30 nm, DBP value 174 ml / 100 g, resistance 100 Ωcm: trade name VXC-72: manufactured by Cabot Corporation) 1500 parts by weight of edge runner “MPUV-2 type” (product name, Matsumoto Foundry, Ltd.) The product was mixed and diluted with 200 parts by weight of ethanol for 50 parts by weight of methyltriethoxysilane (trade name: TSL8123: manufactured by Toshiba Silicone Co., Ltd.), and the edge runner was operated. The mixture was added to the carbon black while mixing and stirring.
[0070]
Next, 150 parts by weight of polyethylene wax PE130 (melting point: 130 degrees, manufactured by Mitsui Chemicals Co., Ltd.) is added over 10 minutes while operating the edge runner, mixed and stirred, and PE130 is coated on the methyltriethoxysilane coating. Then, heat treatment was performed at 105 ° C. for 60 minutes using drying to obtain wax-coated inorganic oxide fine powder C.
The average primary particle size was 36 nm, and the coating state was observed. As a result, the coating thickness was in the range of 1.0 to 3.0, and 100% of the fine powder surface was coated.
[0071]
-Adjustment of wax-coated inorganic oxide fine powder D-
Just by changing the cross-linked melamine resin particles of wax-coated resin fine powder B to conductive powder (average particle size 0.2 μm, resistance 5-30 Ωcm: trade name: Pastoran Type-IV: made by Mitsui Kinzoku Co., Ltd.) A wax-coated inorganic oxide fine powder D was formed. The average particle diameter was 0.2 μm, and the coating state was observed. As a result, the coating thickness was in the range of 0.5 to 2.0 nm, and 100% of the fine powder surface was coated.
[0072]
―Manufacture of Carrier A―
・ Ferrite particles (average particle size 50 μm) ・ ・ ・ ・ 100 parts
・ Toluene ・ ・ ・ 14 parts
・ Perfluorooctyl ethyl acrylate / methyl methacrylate copolymer
(Copolymerization ratio 40:60 Mw = 50,000) ... 1.6 parts
・ Wax coated resin fine powder A ・ ・ ・ ・ 0.3 parts
-Wax-coated inorganic oxide fine powder C-0.12 part
[0073]
The above components excluding the ferrite particles are dispersed with a stirrer for 10 minutes to prepare a film-forming liquid, and the film-forming liquid and ferrite particles are placed in a vacuum degassing kneader and stirred at 60 ° C. for 30 minutes, and then the pressure is reduced. Then, toluene was distilled off, and a film was formed on the surface of the ferrite particles to obtain carrier A.
[0074]
The perfluorooctylethyl acrylate copolymer used as the matrix resin in the coating was obtained because the wax-coated resin fine powder A and the wax-coated inorganic oxide fine powder C were diluted with toluene and dispersed with a sand mill. In the film on the carrier, the wax-coated resin fine powder A and the wax-coated inorganic oxide fine powder C were uniformly dispersed.
[0075]
-Manufacture of carrier B-
A carrier B was obtained by forming a film with the same formulation as Carrier A except that the wax-coated resin fine powder A was changed to the wax-coated resin fine powder B.
[0076]
―Manufacture of Carrier C―
A film was formed by the same formulation as Carrier A except that the wax-coated inorganic oxide fine powder C was changed to the wax-coated inorganic oxide fine powder D to obtain Carrier C.
[0077]
―Manufacture of Carrier D―
A carrier D was obtained by forming a film with the same formulation as Carrier A except that the wax-coated inorganic oxide fine powder C was changed to uncoated carbon black.
[0078]
―Manufacture of Carrier E―
A coating film was formed in the same manner as carrier A except that wax-coated resin fine powder A was changed to uncoated phenol resin particles, and carrier E was obtained.
[0079]
―Manufacture of Carrier F―
A coating film is formed with the same formulation as Carrier A except that the wax-coated resin fine powder A and the wax-coated inorganic oxide fine powder C are changed to uncoated phenol resin particles and uncoated carbon black to obtain carrier particles F. It was.
[0080]
-Manufacture of carrier G-
  Other than removing uncoated phenolic resin particlesCareer FA film was formed with the same formulation as in Example 1, and carrier G was obtained.
[0081]
―Manufacture of Carrier H―
  Except for removing uncoated carbon blackCareer FA film was formed with the same formulation as in Example 1, and Carrier H was obtained.
[0082]
―Manufacture of Carrier I―
A film was formed with the same formulation as Carrier A except that the wax-coated resin fine powder A and the wax-coated inorganic oxide fine powder C were removed to make 2.0 parts by weight of perfluorooctylethyl acrylate / methyl methacrylate copolymer. Carrier I was obtained.
[0083]
[Method for producing colored particle A]
・ Styrene-n-butyl acrylate resin ・ ・ ・ ・ 100 parts
(Tg = 58 ° C., Mn = 4000, Mw = 25000)
・ Cyan pigment Pigment ・ Blue 15: 3 ・ ・ ・ ・ 3 parts
(Mogal L: Cabot)
[0084]
The above mixture is kneaded with an extruder, pulverized with a jet mill, and then dispersed with a wind classifier to obtain a volume average particle diameter D50 = 5.0 μm, SF1 (ML²Black toner A having a / A) of 148.8 was obtained.
[0085]
[Method for producing colored particle B]
<Adjustment of resin dispersion (1)>
・ Styrene ・ ・ ・ ・ 370 parts
-N-butyl acrylate-30 parts
・ Acrylic acid ・ ・ ・ ・ 8 parts
・ Dodecanethiol ・ ・ ・ ・ 24 parts
・ Carbon tetrabromide ・ ・ ・ ・ 4 parts
[0086]
6 parts by weight of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.) and an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 10 parts by weight dissolved in 550 parts by weight of ion-exchanged water was emulsified and dispersed in a flask. While slowly mixing for 10 minutes, 50 parts by weight of ion-exchanged water in which 4 parts by weight of ammonium persulfate had been dissolved was added thereto. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion liquid (1) in which resin particles having an average particle diameter of 155 nm, Tg = 59 ° C., and weight average molecular weight Mw = 12000 was dispersed was obtained.
[0087]
<Adjustment of resin dispersion (2)>
・ Styrene ・ ・ ・ ・ 280 parts
-N-butyl acrylate-120 parts
・ Acrylic acid ・ ・ ・ ・ 8 parts
[0088]
6 parts by weight of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Kasei Co., Ltd.) and an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ) 12 parts by weight dissolved in 550 parts by weight of ion-exchanged water was emulsified and dispersed in a flask. While slowly mixing for 10 minutes, 50 parts by weight of ion-exchanged water in which 3 parts by weight of ammonium persulfate had been dissolved was added. After carrying out nitrogen substitution, the inside of the flask was stirred and heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion liquid (2) in which resin particles having an average particle diameter of 105 nm, Tg = 53 ° C., and weight average molecular weight Mw = 550000 was dispersed was obtained.
[0089]
<Preparation of colored dispersion (1)>
・ Cyan pigment Pigment ・ Blue 15: 3 ・ ・ ・ ・ 70 parts
・ Nonionic surfactant ・ ・ ・ ・ 5 parts
(Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.)
・ Ion exchange water ・ ・ ・ ・ 200 parts
[0090]
A colored dispersion in which the above components are mixed, dissolved, and dispersed for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA) to disperse colorant (Cyan pigment) particles having an average particle diameter of 250 nm. (1) was adjusted.
[0091]
<Preparation of release agent dispersion (1)>
・ Paraffin wax ・ ・ ・ ・ 50 parts
(HNP0190: Nippon Seiwa Co., Ltd., melting point 85 ° C.)
・ Cationic surfactant ・ ・ ・ ・ 5 parts
(Sanisol B50: manufactured by Kao Corporation)
[0092]
The above components were dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes, and then dispersed with a pressure discharge type homogenizer, and the average particle size was 550 nm. A release agent dispersion (1) in which the mold agent particles were dispersed was prepared.
[0093]
<Adjustment of aggregated particles>
・ Resin dispersion (1) ・ ・ ・ ・ 120 parts
・ Resin dispersion (2) ・ ・ ・ ・ 80 parts
-Colored dispersion (1)-200 parts
-Mold release dispersion (1)-40 parts
・ Cationic surfactant ・ ・ ・ ・ 1.5 parts
(Sanisol B50: manufactured by Kao Corporation)
[0094]
The above components were mixed and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA), and then heated to 50 ° C. while stirring the inside of the flask in an oil bath for heating. . After maintaining at 45 ° C. for 20 minutes, it was confirmed with an optical microscope that it was confirmed that aggregated particles having an average particle diameter of about 4.3 μm were formed. Further, 60 parts by weight of the resin dispersion liquid (1) as a resin-containing fine particle dispersion liquid was gradually added to the dispersion liquid. The temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. When observed with an optical microscope, it was confirmed that adhered particles having an average particle diameter of about 4.5 μm were formed.
[0095]
<Preparation of colored particles B>
After adding 3 parts by weight of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to the particle dispersion, the inside of the stainless steel flask is sealed and stirred at 105 ° C. using a magnetic seal. And heated for 4 hours. Then, after cooling, the reaction product is filtered, washed thoroughly with ion-exchanged water, and then dried, so that SF1 (ML²Cyan toner B having a / A) of 130 and a volume average particle diameter D50 = 5.6 μm was obtained.
[0096]
(Examples 1-6 / Comparative Examples 1-4)
Toners A and B (colored particles A and B) were each treated with 1.3 parts of 10% decyltrimethoxysilane with hydrophobic silica (RX50: manufactured by Nippon Aerosil Co., Ltd.) having a volume average primary particle size of 50 nm for 100 parts. 0.7 parts of the titanium oxide having a volume average primary particle size of 20 nm (MT-150A: manufactured by Teika) was mixed for 10 minutes at a peripheral speed of 32 m / s using a Henschel mixer and sieved at 45 μm to remove coarse powder. A toner was obtained.
[0097]
6 parts of the toner and 94 parts of each of carriers A to I were mixed in the combinations shown in Table 2 to prepare developers. Using these electrostatic charge image developers, a copy test was performed with an electrophotographic copying machine (DCC500CP modified machine, manufactured by Fuji Xerox Co., Ltd.). The results are shown in Table 3.
[0098]
[Table 1]

[0099]
[Table 2]

[0100]
[Table 3]

[0101]
【The invention's effect】
As described above, according to the present invention, at least one type of resin particles or conductive particles is dispersed and contained in a coating resin of a carrier in which a core material made of a magnetic material is coated with a resin. The electrostatic image developer carrier characterized in that at least one kind of particles or the conductive particles is coated with a wax, and the developer using the carrier have chargeability, transferability and cleaning properties. Excellent and stable image quality maintenance can be realized.

Claims (6)

In a carrier in which the surface of a core material made of a magnetic material is coated with a resin, one or more kinds of particles selected from resin particles and conductive particles are dispersed and contained in the resin. A carrier for an electrostatic charge image developer, wherein the surface is coated with alkoxysilane, an organosilane compound generated from alkoxysilane or polysiloxane, and a wax component is attached to the coating .   The electrostatic charge image developer according to claim 1, wherein one surface of particles dispersed and contained in the carrier coating resin is coated with a wax component to a thickness of 0.5 to 5 nm. Career. 3. The electrostatic charge image development according to claim 1, wherein 0.1 to 45 parts by weight of the alkoxysilane or polysiloxane is added to 100 parts by weight of the resin particles or conductive particles. Agent carrier. The carrier for an electrostatic charge image developer according to any one of claims 1 to 3, wherein the particles dispersed and contained in the coating resin of the carrier are resin particles made of a nitrogen-containing resin. Particles dispersed contained in the coating resin of the carrier, carbon black, metal, single metal oxide or any one of claims 1 to 3, characterized in that the these complexes, Carrier for electrostatic charge image developer. In the electrostatic charge image developer comprising a carrier and a toner, the toner is a toner having a shape factor SF1 (ML ² / A) in the range of 100 to 140,
The carrier has a coating resin on the surface of a core material made of a magnetic material, and one or more kinds of particles selected from resin particles and conductive particles are dispersed and contained in the resin coating,
One type of the surface of the dispersed particles is coated with alkoxysilane, an organosilane compound generated from alkoxysilane or polysiloxane, and a carrier having a wax component attached to the coating. An electrostatic charge image developer.