JP2014178547A - Toner for electrostatic charge image development, developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that suppresses deterioration of transferability, filming resistance, and toner fluidity, which is a concern in a super high-speed printing system, and stabilizes charging performance.SOLUTION: A toner for electrostatic charge image development includes a toner containing a binder resin, colorant, mold release agent, and charge control agent, and an external additive adhered on the surface of the toner. The charge control agent includes a layered inorganic mineral in which inter-layer ions are modified with organic ions; the external additive includes aspherical insulating inorganic particles having a secondary particle shape formed by a plurality of primary particles being fused with each other; and a relationship between a weight% (A) of the layered inorganic mineral and a weight% (B) of the aspherical insulating inorganic particles satisfies 1.3<B/A<7.0.

Description

  The present invention relates to a developer for developing an electrostatic image formed by electrophotography, electrostatic recording, and the like, a toner used as a developer, and an image forming apparatus including the toner.

  The image forming apparatus includes a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, a developing step for forming an image with toner frictionally charged on the image carrier, The image is fixed on the printing paper after a transfer process in which the image on the image carrier is transferred directly to the printing paper or indirectly via an intermediate transfer body. Further, the untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process, and enters the next image forming process.

  In recent years, in order to achieve energy saving, in order to lower the glass transition temperature, a toner that can be fixed at a lower temperature than before has been produced by using crystalline polyester as a binder resin. However, since crystalline polyester has high hygroscopicity, a toner used after being left in a high-temperature and high-humidity environment cannot obtain a sufficient charge amount, and it is difficult to obtain a good image density. Moreover, since it melts at a low temperature, the storage stability tends to deteriorate in a high temperature environment. The compatibility between low-temperature fixability and storage stability and charging stability are major issues.

  In order to improve the storage stability, by using wet-process silica that can be controlled to a larger particle size than dry-process silica, a spacer effect is provided to prevent contact between toners. A crystalline resin and a silica-containing toner treated with silicone oil and having an average primary particle size of 50 nm to 150 nm have been proposed (Patent Document 1). However, since this range of particle diameter includes silica having a large particle diameter of 120 to 150 nm, it is considered that an abnormal image due to the liberation of silica is likely to occur as described above.

  However, due to stress with the developer, silica is likely to be liberated, and the spent to the carrier is likely to occur, so that it is likely to cause a significant decrease in charge and also to be spent on the photoconductor. There is also concern about the occurrence of such abnormal images. Furthermore, there is a problem that the spacer effect is lost when silica is embedded in toner particles due to stress.

In order to prevent such liberation and burial of silica, liberation and burial are suppressed by making silica non-spherical and increasing the contact area with the base particles (Patent Document 2).
Compared with dry-process silica, wet-process silica has a relatively low electrical resistance even when the hydrophobization treatment is performed and the apparent hydrophobization rate is high, and the particle size is also large compared with dry-process silica. The toner surface is likely to be a charge injection site, and a charge change due to a transfer electric field is likely to occur. In addition, since the internal structure is more porous and contains a large amount of adsorbed moisture, the charge level is low (Patent Document 3).

  On the other hand, a combination of silica and a charge control agent that lowers the charge level has already been implemented. In addition, it is known that the charge level lowering due to the use of non-spherical inorganic particles such as silica is compensated by a charge control agent, and when the charge level is high, the addition amount of non-spherical inorganic particles is compensated. As a charge control agent, it is known that when a metal salt of salicylic acid or a metal salt of a salicylic acid derivative is used for a toner, a necessary charge amount can be obtained (Patent Document 4).

  However, there is an explanation for one specific quantity, but the relation between both specific quantities is not sufficient.

  In view of the above-described problems of the prior art, the present invention provides an electrostatic charge image developing toner that is stabilized in charge by suppressing deterioration in transferability, filming resistance, and toner fluidity, which are feared in an ultrahigh-speed printing system. The purpose is to provide.

  As a result of intensive studies, the present inventors have used a charge control agent containing a specific layered inorganic mineral and an external additive containing a specific insulating inorganic particle, and the layered inorganic mineral and the insulating inorganic particle are predetermined. The present inventors have found that the above problems can be solved by satisfying the ratio.

That is, the present invention relates to an electrostatic charge image developing toner in which an external additive adheres to the surface of a toner containing a binder resin, a colorant, a release agent, and a charge control agent. A layered inorganic mineral in which interlayer ions are modified with organic ions, and the external additive includes non-spherical insulating inorganic particles in the form of secondary particles in which a plurality of primary particles are coalesced, and the weight of the layered inorganic mineral % (A) and the weight% (B) of the non-spherical insulating inorganic particles satisfy the following formula (i): an electrostatic charge image developing toner.
1.3 <B / A <7.0 Formula (i)

  According to the present invention, it is possible to provide a toner for developing an electrostatic charge image that suppresses deterioration in transferability, filming resistance, and toner fluidity, which are feared in an ultra-high-speed printing system, and stabilizes charging.

It is the schematic which shows an example of the secondary particle diameter of a silica. 1 is a schematic diagram illustrating an example of an image forming apparatus used in the present invention. It is the schematic which shows the other example of the image forming apparatus used by this invention. It is the schematic which shows the further another example of the image forming apparatus used by this invention. FIG. 5 is a schematic diagram illustrating a part of the image forming apparatus illustrated in FIG. 4.

  A desired charge level can be obtained by adding appropriate amounts of insulating inorganic particles and a charge control agent to the toner. It is possible to control the charge by adding appropriate amounts of conductive inorganic particles and a charge control agent to the toner, but the improvement in fluidity, developability, storage stability, etc. as other toners cannot be expected. Insulating inorganic particles can be used effectively. Insulating inorganic particles include silica and alumina, but the negative charge amount increases as the electronegativity of the metal ions constituting the oxide increases. Therefore, in the present invention, silica that can be easily charged is controlled. It can be particularly preferably used. Further, improvement and improvement of fluidity, developability, chargeability, storage stability, etc. can be expected.

  As a method for producing silica, a technique generally called a sol-gel method or a dry method is used. Silica produced by the sol-gel method has the characteristics of high moisture content, volume resistance, sharp particle size distribution, and excellent moisture adsorptivity.

However, as a side effect, the silica derived from the sol-gel method has a relatively low electric resistance even if the apparent hydrophobization rate is increased by performing the hydrophobization treatment. In addition, since the particle diameter is larger than that of dry silica, it is likely to be a charge injection site on the toner surface, and a charge change due to a transfer electric field is likely to occur. Further, since the internal structure is more porous and contains a large amount of adsorbed moisture, the charge level is lowered. On the other hand, silica produced by a dry method has a characteristic that the particle size distribution is relatively broad but has a very low water content and a strong negative chargeability, and thus has a high charging ability.
Moreover, it can be expected that the crystalline polyester and the external additive silica are used in combination to improve the low-temperature fixability of the crystalline polyester and the accompanying deterioration in storage stability.
In order to improve the storage stability, the amount of silica added is increased to improve the storage stability, or silica having a large particle diameter derived from the sol-gel method is added to prevent contact between toners by the spacer effect. In this case, however, fluidity is lowered and charging property is deteriorated, and image blurring due to photoconductor filming is caused.

  However, the secondary particle size of the additive covering the toner is 80 to 200 nm using silica derived from a sol-gel method which is a non-spherical secondary particle shape in which a plurality of primary particles are coalesced as in the present invention. This suppresses the embedding in the toner and improves the fluidity. In addition, filming resistance is improved because separation from the toner is reduced as compared with silica having a particle diameter larger than 200 nm. Silica having a particle diameter larger than 200 nm is detached from the toner due to its own size, so that the desired spent resistance and filming resistance cannot be obtained. Further, when the external additive is buried in the toner or separated from the toner, a transfer defect occurs.

From the above, regarding the relationship between the amount of the charge control agent of the present invention and the non-spherical insulating inorganic particles, the inorganic particles have a particle size, fluidity, chargeability, transfer stability, Non-spherical silica that contributes to filming properties is particularly preferred.
In the following description, silica is used as the inorganic particles. However, the present invention is not limited to silica, and alumina or the like can also be used.

  The silica derived from the sol-gel method is an additive for reducing the charge level, which is reduced when compared with the charge amount of the base particles alone when mixed with the base particles. On the other hand, silica derived from the dry process is an additive for increasing the charge level, which is increased when compared with the charge amount of the base particles alone when mixed with the base particles. This reduction in charge level is adjusted to a desired charge level with a charge control agent. When the charge level is high, the desired charge level is adjusted with the addition amount of silica. As a charge control agent, it is known that when a metal salt of salicylic acid or a metal salt of a salicylic acid derivative is used in a toner, a necessary charge amount can be obtained.

In the present invention, the charge control agent preferably contains a layered inorganic mineral obtained by modifying interlayer ions with organic ions. Moreover, it is preferable that the external additive includes non-spherical insulating inorganic particles having a secondary particle shape in which a plurality of primary particles are coalesced. In the present invention, the weight% (A) of the layered inorganic mineral and the weight% (B) of the non-spherical inorganic particles satisfy the following formula (i).
1.3 <B / A <7.0 Formula (i)
When 7.0 ≦ B / A is satisfied with respect to 1.3 <B / A <7.0, which is the relationship between the weight% (A) of the layered inorganic mineral and the weight% (B) of the non-spherical inorganic particles, In the case of the method-derived, the amount of silica added to the charge control agent is increased. Therefore, the desired charge level is not reached due to the decrease in the charge level. Although the addition amount of the charge control agent can be increased, there is a concern that the fluidity of the toner is lowered. Further, since the amount of silica added is increased, there is a concern about filming on the photoreceptor, spent spent on external additives on the carrier, and deterioration of charging stability.

  On the other hand, in the case of silica derived from the dry process, when 7.0 ≦ B / A, the amount of silica added is larger than that of the charge control agent, so the level of charge level becomes high and the desired charge level is reduced. It will exceed. Moreover, since the amount of silica added increases, there is a concern about the same problem as that of silica derived from the sol-gel method.

  When B / A ≦ 1.3, the amount of silica is small, and in the case of silica derived from the sol-gel method, the level of charge amount is too high. The chargeability of the toner is too great, and the electrostatic attractive force with the developing roller increases, leading to a decrease in developer fluidity and a decrease in image density. Further, by reducing the addition amount, it becomes easy to be affected by the release or burying of the external additive due to the stress over time, and there is a possibility that the transfer stability and the charging stability are lost.

  On the other hand, in the case of silica derived from the dry process, the charge change does not occur as much as the silica derived from the sol-gel process when B / A ≦ 1.3. However, considering compatibility with storage stability, it is not preferable that the particle size of the additive is small, so that reducing the addition amount weakens the spacer effect and increases the contact between the toners.

  It is more preferable that 1.7 <B / A <6.4 than 1.3 <B / A <7.0. When B / A <7.0, the desired charge level is reached regardless of the silica production method, but there is no margin because of the upper and lower limits of the desired charge level. By setting B / A <6.4, in addition to improving the margin of charge level, the fluidity of the toner, which is a concern for the amount of silica added, filming on the photoreceptor, and spent spent on external additives on the carrier The margin for is improved. On the other hand, when 1.3 <B / A, the margin of heat-resistant storage stability and transfer stability becomes small as described above. By setting 1.7 <B / A, the heat resistance storage stability and the margin of transfer stability are improved.

The non-spherical insulating inorganic particles preferably include non-spherical coalesced particles obtained by coalescing primary particles and satisfy the following formula (ii).
Nx / 1000 × 100 ≦ 30 [%] Formula (ii)
In the formula (ii), Nx represents the number of cracked or disintegrated particles in 1,000 of the non-spherical insulating inorganic particles.
The number of cracked or disintegrated particles in 1,000 of the non-spherical insulating inorganic particles is 0.5 g of the non-spherical insulating inorganic particles and 49.5 g of the carrier placed in a 50 mL bottle. After stirring with a rocking mill under conditions of 67 Hz for 10 minutes, it can be determined by observing with a scanning electron microscope.
The non-spherical insulating inorganic particles preferably satisfy the following formula (iii).
Db50 / Db10 ≦ 1.20 Formula (iii)
However, in the formula (iii), the average particle diameter of the 50th number% measured from the small particle side of the secondary particle diameter Db observed by FE-SEM (field emission scanning electron microscope) is Db50, the small particle side The average particle diameter of the 10th number% measured from the above is defined as Db10.
The average secondary particle diameter Db of the non-spherical insulating inorganic particles is preferably in the range of 80 nm to 200 nm.

In the toner of the present invention, the binder resin component preferably contains a binder resin precursor. The toner of the present invention is obtained by dissolving and dispersing at least a colorant, a release agent, a binder resin precursor containing a modified polyester resin, and other binder resin components in an organic solvent. After dissolving the binder resin precursor and a compound that extends or crosslinks in the oil phase, the oil phase is dispersed in an aqueous medium in which a fine particle dispersant is present to obtain an emulsified dispersion, and the emulsified dispersion And a toner obtained by removing the organic solvent by subjecting the binder resin precursor to a crosslinking reaction and / or elongation reaction.
The toner of the present invention preferably contains a crystalline resin and an amorphous resin as a binder resin.

(Binder resin precursor)
As the binder resin precursor, a binder resin precursor made of a modified polyester resin is preferable, and examples thereof include a polyester prepolymer modified with isocyanate or epoxy. This undergoes an extension reaction with a compound having an active hydrogen group (such as amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset generation temperature). As a method for synthesizing the polyester prepolymer, the polyester prepolymer can be easily synthesized by reacting a base polyester resin with a conventionally known isocyanate agent or epoxidizing agent.

Isocyanating agents include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (Tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; block the polyisocyanates with phenol derivatives, oximes, caprolactam, etc. And combinations of two or more of these.
Moreover, epichlorohydrin etc. can be mentioned as the representative example as an epoxidizing agent.

The ratio of the isocyanate agent is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the base polyester. 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the urea content of this polyester prepolymer becomes low, and the hot offset resistance deteriorates.
The content of the isocyanate agent in the polyester prepolymer is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the polyester prepolymer is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester resin after the elongation reaction is lowered, and the hot offset resistance is deteriorated.
The binder resin precursor preferably has a weight average molecular weight of 1 × 10 ⁴ or more and 3 × 10 ⁵ or less.

(Compound that stretches or crosslinks with binder resin precursor)
Examples of the compound that extends or crosslinks with the binder resin precursor include compounds having an active hydrogen group, and typical examples thereof include amines. Examples of amines include diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked.
Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine). Etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan compound include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of amino acid compounds include aminopropionic acid and aminocaproic acid.
Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines, preferred are a diamine compound and a mixture of a diamine compound and a small amount of a polyamine compound.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Se Red, Para Chlorortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
The release agent is preferably a wax having a melting point of 50 to 120 ° C.
Since such a wax can effectively act as a release agent between the fixing roller and the toner interface, high temperature offset resistance can be improved without applying a release agent such as oil to the fixing roller. be able to.
The melting point of the wax can be obtained by measuring the maximum endothermic peak using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation), which is a differential scanning calorimeter.

As the mold release agent, the following materials can be used.
As waxes and waxes, plant waxes such as carnauba wax, cotton wax, wood wax, rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, petrolatum, etc. And petroleum wax.
In addition, examples of mold release agents other than these natural waxes include synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; and synthetic waxes such as esters, ketones, and ethers.
Furthermore, fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymer, poly (n-stearyl methacrylate), poly (methacrylic acid n) -A crystalline polymer having a long-chain alkyl group in the side chain, such as a homopolymer or copolymer of polyacrylate such as lauryl (for example, n-stearyl acrylate-ethyl methacrylate copolymer) is also used as a release agent. Can do.

(Charge control agent)
All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts.
Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
The metal salt of salicylic acid or a salicylic acid derivative that is preferably used as a charge control agent in the present invention can be represented by the following general formula (1).

However, R < ³ >, R < ⁴ > and R < ⁵ > represent a hydrogen atom or a C1-C10 alkyl group or an aryl group, respectively. Me represents any metal atom selected from zinc, nickel, cobalt, lead and chromium.

  The amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method. Therefore, although it is not uniquely limited, Preferably it is used in 0.1-10 weight part with respect to 100 weight part of binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with the masterbatch and resin, or of course, may be added when directly dissolving and dispersing in an organic solvent.

  When it is added when dissolved or dispersed directly in an organic solvent, it is encapsulated in the toner particles, and the vicinity of the surface of the toner (from the toner surface toward the center of the toner, any point on the toner surface and the center of the toner are The concentration of the charge control agent that exists from the inner portion (the portion from the inner dividing point to the center of the toner) and in the vicinity of the toner surface. However, the concentration is preferably larger than the concentration of the charge control agent present in the toner.

(Layered inorganic mineral)
The charge control agent contained in the toner of the present invention contains a layered inorganic mineral in which interlayer ions are modified with organic ions. A layered inorganic mineral refers to an inorganic mineral formed by overlapping layers having a thickness of several nanometers, and modifying with organic ions means introducing organic ions into ions existing between the layers. This is called intercalation in a broad sense.

  The layered inorganic mineral modified with organic ions may be referred to as a modified layered inorganic mineral, and the organic ions for modifying the layered inorganic mineral may be referred to as an organic ion modifier. In addition, ions existing between layers of the layered inorganic mineral may be referred to as interlayer ions.

  As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. For this reason, if the layered inorganic mineral is used in a toner that is dispersed and granulated in an aqueous medium without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. Therefore, the hydrophilicity is increased by modification, and such a modified layered inorganic mineral is refined and deformed during the production of the toner, and is particularly present in the surface portion of the toner particle, and performs a charge control function, and at a low temperature. It also contributes to fixing.

  As the modified layered inorganic mineral, one having a smectite basic crystal structure modified with an organic cation is desirable. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable when the metal anion is introduced.

  In the present invention, a layered inorganic mineral obtained by modifying at least a part of interlayer ions of the layered inorganic mineral with organic ions is used, and one of typical examples thereof is an organically modified clay. Furthermore, this includes, for example, organically modified clay in which a layered inorganic mineral such as clay is anionic and modified with an organic cation. Further, the layered inorganic mineral is hydrotalcite, which is cationic and includes organic modified hydrotalcite modified with an organic anion.

  The organically modified clay used in the toner of the present invention is preferably one having a smectite basic crystal structure modified with an organic cation. Examples of the layered inorganic mineral modified with an organic cation include montmorillonite or bentonite, beidellite, nontronite, saponite, hectorite and the like.

  Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable.

  Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates, or phosphates having Among these, a carboxylic acid having an ethylene oxide skeleton is desirable.

  By modifying at least a part of the layered inorganic mineral with organic ions, the layered inorganic mineral has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, Can be modified. The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among them, montmorillonite or bentonite partially modified with organic ions is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the amount added can be reduced.

  Examples of commercially available layered inorganic minerals in which at least a part of metal cations such as Al, K, Mg, and Ca of the layered inorganic mineral are modified with an organic cation include Bentone 3, Bentone 38, and Bentone 38V (above, manufactured by Leox Corporation). ), Thixogel VP (manufactured by United Catalyst), Clayton 34, Clayton 40, Clayton XL, Clayton AF, Clayton APA (above, manufactured by Southern Clay), etc .; (Catalyst), Clayton AF, Clayton APA (above, Southern Clay) and other stearalkonium bentonites; Clayton HT, Clayton PS (above, Southern Clay) etc. Nium 18 / benzalkonium bentonite. Particularly preferable examples include Clayton AF and Clayton APA.

  Other examples include BENTONE34, BENTONE52, BENTONE27, BENTONE57, BENTONESD57, BENTONESD2, BENTONESD3, etc. manufactured by ELEMENTIS, CRAYTON HT, CRAYTONE 2000 manufactured by SCP, E, Esven C, Esben NZ, Esben NZ70, Esben W, Esben N400, Esben NX, Esven NX80, Esven NO12S, Esven NEZ, Esven NO12, Esven WX, Esven NE, etc. Knives 127 etc. are mentioned.

Further, as the layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (2) is particularly preferable. The following general formula (2) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
_{^{R 1 (OR 2) nOSO 3}} M ··· formula (2)
[Wherein, R ¹ represents an alkyl group having 13 carbon atoms, and R ² represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element. ]

  By using the modified layered inorganic mineral, it has moderate hydrophobicity, and the oil phase containing the toner composition has a non-Newtonian viscosity in the production process of the toner having this, and the toner can be deformed.

(Non-crystalline polyester resin)
In the present invention, an amorphous unmodified polyester resin can be used as the binder resin component. It is preferable that at least a part of the modified polyester resin obtained by crosslinking and / or elongation reaction of the binder resin precursor made of the modified polyester resin is compatible with the unmodified polyester resin. Thereby, low temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid of the modified polyester resin and the unmodified polyester resin have similar compositions. Further, as the unmodified polyester resin, the non-modified polyester resin used in the crystalline polyester dispersion can also be used as long as it is unmodified.

The acid value of the unmodified polyester resin is usually 1 to 50 KOHmg / g, preferably 5 to 30 KOHmg / g. As a result, since the acid value is 1 KOHmg / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved at the time of fixing to the paper, and the low-temperature fixability can be improved. . However, if the acid value exceeds 50 KOHmg / g, the charging stability, particularly the charging stability against environmental fluctuations, may be reduced. In the present invention, the unmodified polyester resin preferably has an acid value of 1 to 50 KOHmg / g.
The hydroxyl value of the unmodified polyester resin is preferably 5 KOHmg / g or more.

The hydroxyl value can be measured using a method based on JIS K0070-1966.
As a specific example, first, 0.5 g of a sample is precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1-2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used.

At this time, examples of measurement conditions are as follows.
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to
volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium
controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump
only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination
conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

  The urea-modified polyester resin can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified polyester resin.

When the toner composition contains a modified polyester resin such as a urea-modified polyester resin, the modified polyester resin can be produced by a one-shot method or the like.
As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, a urea pre-modified polyester resin can be obtained by reacting a polyester prepolymer having an isocyanate group with amines at 0 to 140 ° C.

The number average molecular weight of the urea-modified polyester resin is usually 1,000 to 10,000, and preferably 1,500 to 6,000.
In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.
Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.
In addition, when using unmodified polyester resin together, you may mix to the solution after reaction of the urea modified polyester resin what was manufactured similarly to the polyester resin which has a hydroxyl group.

In the present invention, as the binder resin component contained in the oil phase, a crystalline polyester resin, an amorphous polyester resin, a binder resin precursor, and an unmodified resin may be used in combination. The binder resin component may be contained. The binder resin component preferably contains a polyester resin, and more preferably contains 50% by weight or more of the polyester resin. If the content of the polyester resin is less than 50% by weight, the low-temperature fixability may be lowered. It is particularly preferable that all of the binder resin components are polyester resins.
Examples of binder resin components other than polyester resins include polystyrene, poly (p-chlorostyrene), styrene-substituted polymers such as polyvinyltoluene, styrene-substituted polymers, styrene-p-chlorostyrene copolymers, and styrene-propylene copolymers. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; Methyl acid, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The binder resin precursor, colorant, release agent, crystalline polyester dispersion, charge control agent, unmodified polyester resin, etc. that form toner particles are mixed when forming the dispersion in an aqueous medium. Also good. However, it is more preferable to mix these toner raw materials in advance and then add and disperse the mixture in an aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of revolutions is not particularly limited, but is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 60 minutes. The temperature during dispersion is usually 0 to 80 ° C. (under pressure), preferably 10 to 40 ° C.

  The amount of the aqueous medium used is usually 100 to 1,000 parts by weight with respect to 100 parts by weight of the toner composition. If the amount is less than 100 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 1,000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  As a method of reacting the polyester prepolymer and the compound having active hydrogen groups, the compound having active hydrogen groups may be added and reacted before dispersing the toner composition in the aqueous medium. Moreover, after dispersing in an aqueous medium, a compound having an active hydrogen group may be added to cause a reaction from the particle interface. In this case, a polyester modified with a polyester prepolymer is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamines, etc. as dispersants for emulsifying and dispersing the oil phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl- Amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount.
Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts thereof, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid or organic fine particles insoluble in water. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group, For example, vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc. can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner to wash away after the reaction.

Further, in order to lower the viscosity of the toner composition, a solvent in which the polyester prepolymer reacts and is modified with a modified polyester can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.
In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 parts of polyester prepolymers is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the polyester prepolymer and the compound having an active hydrogen group, and is usually 10 minutes to 40 hours, preferably 30 minutes to 24 hours. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C. Moreover, a well-known catalyst can also be used as needed. Specific examples include tertiary amines such as triethylamine and imidazoles.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer, rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.

The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder Immobilize and fuse on the surface. Thereby, detachment | disassembly of the different particle | grains from the surface of the composite particle obtained can be prevented.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability, storage stability and the like to the toner particles. The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Silicon, silicon nitride, or the like can be used. These may be used individually by 1 type and may use 2 or more types together.
In the present invention, the external additive described above includes non-spherical insulating inorganic particles having a secondary particle shape in which a plurality of primary particles are coalesced. As the non-spherical insulating inorganic particles, silica produced by a sol-gel method is more preferable.
The fused silica is obtained by chemically bonding primary particles of silica and / or fused silica using a treating agent, and the silica obtained by secondary aggregation is referred to as fused silica.

The fused silica used in the present invention can be prepared by chemically bonding primary particles of crystalline silica and / or fused silica using a treating agent. As the treatment agent, silane treatment agents such as alkoxysilanes, silane coupling agents, chlorosilanes, and silazanes, or epoxy treatment agents such as liquid epoxy resins are preferably used.
When the silica primary particles are treated with a silane treatment agent such as alkoxysilanes or silane coupling agents, silanol groups bonded to the silica primary particles react with alkoxy groups bonded to the silane treatment agent. A new Si—O—Si bond is formed by dealcoholization.
That is, as shown in the following formula, the silica primary particles are secondarily aggregated by chemical bonding via the silane-based treatment agent.

  When silica primary particles are treated with chlorosilanes, chloro groups of chlorosilanes and silanol groups bonded to the silica primary particles form new Si—O—Si bonds by dehydrochlorination, When water coexists in water, chlorosilanes are first hydrolyzed to form silanol groups, and the silanol groups and the silanol groups bonded to the silica primary particles are each renewed with new Si-O-Si by dehydration reaction. Bonds are formed and secondary aggregation occurs.

Silazanes are agglomerated secondary by generating new Si—O—Si bonds by deammoniation of amino groups and silanol groups bonded to silica primary particles.
On the other hand, when silica primary particles are treated with an epoxy-based treatment agent, silanol groups bonded to the silica primary particles add an epoxy group oxygen atom of the epoxy-based treatment agent and a carbon atom bonded to the epoxy group. Then, a new Si—O—C bond is formed.
That is, as shown in the following formula, the silica primary particles are secondarily aggregated by a chemical bond via an epoxy-based treatment agent.

  The fused silica used in the present invention is prepared by preparing silica as primary particles, and then preparing fused silica by treating the silica with the above-described silane-based treatment agent or epoxy-based treatment agent to fill the epoxy resin. However, for example, when silica is synthesized by a sol-gel method, a fused silica may be prepared by a one-step reaction in the presence of the silane-based treatment agent or epoxy-based treatment agent.

  In addition, since the Si—O—Si bond to be produced is more stable to heat than the Si—O—C bond, the silane-based treatment agent is more preferable than the epoxy-based treatment agent. desirable. Specific examples of alkoxysilanes that are the silane-based treatment agents include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Examples include methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane.

Specific examples of the silane coupling agent that is the silane treatment agent include γ-aminopropyltolethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxy. Examples include silane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, and methylvinyldimethoxysilane.
Further, as silane-based treatment agents other than the above alkoxysilanes or silane-based coupling agents, specifically, vinyltrichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N, N Examples include '-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, and cyclosilazane mixture.

Specific examples of the epoxy-based treatment agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and biphenol type epoxy. Examples thereof include resins, glycidylamine type epoxy resins, and alicyclic epoxy resins.
The fused silica used in the present invention is prepared by chemically bonding primary particles of crystalline silica and / or fused silica using the above-mentioned treatment agent. The treatment is performed by first combining the primary silica particles and the treatment agent. Mixing is performed at a weight ratio of 100: 0.01 to 100: 50 using a known mixer such as a spray dryer.
At that time, for example, water or a 1% aqueous acetic acid solution may be appropriately added as a processing aid. The mixture of the silica primary particles and the treatment agent is then fired, and the firing temperature is preferably in the temperature range of 100 to 2500 ° C. The firing time is preferably 0.5 to 30 hours.

The degree of coalescence of silica can be arbitrarily controlled by adjusting the primary particle diameter, the type and amount of the treatment agent, and the treatment conditions.
That is, the cohesive strength is stronger when a silane-based treatment agent is used than when an epoxy-based treatment agent is used, when the amount of the treatment agent is increased with respect to the silica primary particles, and when the firing temperature is higher. And the degree of adhesion tends to be high.
The degree of coalescence is preferably in the range of 1.5 to 4.0, more preferably 1.7 to 3.5. When this is smaller than 1.5, the transferability cannot be maintained because the external additive is easily embedded in the base material and the external additive easily rolls into the recess. On the other hand, when the ratio is larger than 4.0, the external additive is easily peeled off from the toner, resulting in image defects over time due to a decrease in charge due to carrier contamination and generation of scratches on the photoreceptor.

(Measurement of degree of adhesion)
The measurement of the degree of adhesion is obtained by image observation. After the fused silica is dispersed in a suitable solvent (such as THF), the solvent is removed from the substrate and dried, and the sample is observed with an FE-SEM. The secondary particle diameter is measured for silica in the field of view at an acceleration voltage of 5 to 8 kV and an observation magnification of 8 to 10 k times. The secondary particle diameter can be obtained by measuring the longest length of the aggregated particles. An example is shown in FIG. In FIG. 1, the length of the arrow in the figure is the secondary particle diameter.
The number of silica to be observed is 100 or more particles. The primary particle diameter is determined by measuring the BET specific surface area and using the BET specific surface area diameter calculated from the BET specific surface area.
The BET specific surface area of silica can be measured using an automatic specific surface area / pore distribution measuring device (TriStar 3000: manufactured by Shimadzu Corporation). About 0.4 g of the sample was weighed in the sample cell, and this was vacuum-dried with a pretreatment smart prep (manufactured by Shimadzu Corporation) for 24 hours to remove impurities and moisture on the sample surface. The pretreated sample is set in TriStar 3000, and the relationship between the nitrogen gas adsorption amount and the relative pressure is obtained. From this relationship, the BET specific surface area of the sample can be obtained by the BET multipoint method.

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

(Career)
Hereinafter, the carrier that can be used in the present invention will be described in detail.
As the basic structure of the carrier in the present invention, the basic structure of the carrier in the present invention is composed of a core material particle having magnetism and a resin layer covering the surface thereof. The selection of the particle size is important. As a carrier that can be used in the developing method of the present invention, the weight average particle diameter Dw is in the range of 20 to 45 μm. When the weight average particle diameter Dw is larger than the above range, carrier adhesion is less likely to occur, but the toner is not developed faithfully with respect to the electrostatic latent image, and the variation in the dot diameter increases and graininess (roughness). Decreases.
In addition, when a carrier having a weight average particle diameter Dw smaller than 20 μm is used, particles with small magnetization are present throughout the magnetic brush, and the carrier adhesion is rapidly deteriorated.
Further, in the carrier particles having a weight average particle diameter Dw of 22 to 32 μm, sharp particles in which particles smaller than 36 μm are 80% by weight or more, more preferably 82% by weight or more and the content of particles smaller than 44 μm are 90% by weight or more. A carrier coated with a resin having a particle size distribution has a small variation in magnetization of each carrier particle, and carrier adhesion can be greatly improved by a developing method in which a DC bias is applied.

In particular, the content of particles having a particle size smaller than 20 μm is in the range of 0-7 wt%, the content of particles smaller than 36 μm is 80-100 wt%, and the content of particles smaller than 44 μm is 90-100 wt%. A carrier coated with a resin having a sharp particle size distribution becomes smaller in variation in magnetization of each carrier particle, and can greatly improve carrier adhesion.
Further, in the carrier particles having a weight average particle diameter Dw of 22 to 32 μm, sharp particles in which particles smaller than 36 μm are 80% by weight or more, more preferably 82% by weight or more and the content of particles smaller than 44 μm are 90% by weight or more. A carrier coated with a resin having a particle size distribution has a small variation in magnetization of each carrier particle, and carrier adhesion can be greatly improved by a developing method in which a DC bias is applied.

  Further, the carrier used in the present invention is preferably a carrier having a sharper particle size distribution and uniform particle size, and in addition to the above-mentioned regulation of the weight average particle diameter Dw, the carrier and the carrier regulated by the number average particle diameter Dp. Preferably, core material particles are used.

As a particle size analyzer for measuring the particle size distribution in the present invention, a Microtrac particle size analyzer (model HRA9320-X100: manufactured by Honeywell) was used.
In addition, the carrier according to the present invention requires a predetermined magnetization because of the need to form a magnetic brush. The amount of magnetization of such a carrier is the magnetization when a magnetic field of 1,000 Oersted (Oe) is applied. The amount is 40-100 emu / g, more preferably 50e-90 mu / g. When it becomes less than 40 emu / g, carrier adhesion tends to occur, and when it becomes 100 emu / g or more, the head trace of the magnetic brush becomes strong.
The amount of magnetization can be measured as follows. Using a BH tracer (BHU-60 / manufactured by Riken Denshi Co., Ltd.), 1 g of carrier core particles are packed in a cylindrical cell and set in an apparatus. The magnetic field is gradually increased and changed to 3,000 Oersted, then gradually decreased to zero, and then the opposite magnetic field is gradually increased to 3,000 Oersted. Further, after gradually reducing the magnetic field to zero, a magnetic field is applied in the same direction as the first. In this way, a BH curve is drawn, and a 1,000 Oersted magnetic moment is calculated from the drawing.

  The amount of magnetization of such carriers is basically determined by the magnetic material that becomes the core particles. Examples of the core particles that are 40 emu / g or more when a 1,000 oersted magnetic field used in the carrier of the present invention is applied include, for example, ferromagnetic materials such as iron and cobalt, magnetite, hematite, Li-based ferrite, Examples thereof include MnZn ferrite, CuZn ferrite, NiZn ferrite, Ba ferrite, and Mn ferrite.

  The core particles used in the carrier of the present invention are crushed particles of magnetic material, or in the case of core materials such as ferrite and magnetite, the primary granulated product before classification is classified, and the sintered particles are classified. It can be obtained by mixing a plurality of particle powders after classification into particle powders having different particle size distributions by treatment.

As a method of classifying the core particles, conventionally known classification methods such as a sieving machine, a gravity classifier, a centrifugal classifier, and an inertia classifier can be used, but the productivity is easy and the classification point can be easily changed. Therefore, it is preferable to use an air classifier such as a gravity classifier, a centrifugal classifier, or an inertia classifier.
In the carrier of the present invention, the electrical resistivity (log R) is preferably in the range of 11.0 to 17.0 Ω · cm, and more preferably in the range of 11.5 to 16.5 Ω · cm. When the resistivity logR of the carrier is less than 11.0 Ω · cm, when the developing gap (the closest distance between the photosensitive member and the developing sleeve) becomes narrow, charges are induced in the carrier and carrier adhesion is likely to occur. If it exceeds 17.0 Ω · cm, the edge effect becomes stronger and the image density of the solid image portion becomes lower. On the other hand, when LogR is greater than 17.0 Ω · cm, charges having the opposite polarity to the toner are likely to be accumulated, and the carrier is charged and carrier adhesion is likely to occur.

The resistivity of the carrier can be adjusted by adjusting the resistance of the coating resin on the core particles and controlling the thickness of the coating layer. Moreover, it is also possible to add conductive fine powder to the coating resin layer for carrier resistance adjustment. Examples of the conductive fine powder include conductive metals such as ZnO and Al, or cerium oxide, alumina, for example, metal oxides such as SiO ₂ and TiO ₂ having a hydrophobic surface, SnO ₂ prepared by various methods, and various _{SnO 2, TiB 2, ZnB 2} , borides such as MoB ₂ that doped with elements, silicon carbide, polyacetylene, polyparaphenylene, poly (para - phenylene sulfide) polypyrrole, a conductive polymer such as polyethylene, furnace black, Examples thereof include carbon black such as acetylene black and channel black.
These conductive fine powders can be obtained by the following methods: a dispersing machine using a medium such as a ball mill or a bead mill after the conductive fine powder is put into a solvent used for coating or a resin solution for coating, or a blade rotating at high speed. The dispersion for forming a coating layer is prepared by uniformly dispersing by using a stirrer equipped with, and the carrier can be prepared by applying the dispersion for forming a coating layer to the core material particles.
As the resin used for the carrier coating layer, various conventionally known resins can be used, and a silicone resin is preferably used.

In the present invention, a straight silicone resin can be used as the silicone resin. Examples thereof include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2406 (manufactured by Toray Dow Corning Silicone).
In the present invention, a modified silicone resin can be used as the silicone resin. Examples of such materials include epoxy-modified silicone, acrylic-modified silicone, phenol-modified silicone, urethane-modified silicone, polyester-modified silicone, and alkyd-modified silicone. Specific examples of the modified silicone resin include epoxy modified product: ES-1001N, acrylic modified silicone: KR-5208, polyester modified product: KR-5203, alkyd modified product: KR-206, urethane modified product: KR-305 ( As mentioned above, Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

Furthermore, in this invention, it is also possible to use the resin shown below individually or in mixture with the said silicone resin.
Polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, Styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer) Polymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylate copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, Styrene-phenyl methacrylate copolymer, etc.) Styrenic resins such as styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, epoxy resin, polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, ketone resin, ethylene -An ethyl acrylate copolymer, a xylene resin, a polyamide resin, a phenol resin, a polycarbonate resin, a melamine resin, a fluorine resin, or the like can be suitably mixed with the silicone resin.
In the present invention, a carrier having good durability can be obtained by adding an aminosilane coupling agent to the coating layer made of the silicone resin.
The aminosilane coupling agent used in the present invention is preferably 0.001 to 30% by weight.

As a method for forming the resin coating layer on the surface of the carrier core material particles, a known method such as a spray drying method, a dipping method, or a powder coating method can be used. In particular, the method using a fluidized bed type coating apparatus is effective for forming a uniform coating layer.
The thickness of the coating layer on the surface of the carrier core particles is usually 0.02-1 μm, preferably 0.03-0.8 μm. Since the thickness of the coating layer is extremely small, the carrier having the coating layer formed on the surface of the core particle and the carrier core particle have substantially the same particle size.
In this case, the carrier bulk density affects the carrier adhesion, but the carrier bulk density recommended in the present invention is 2.15 to 2.70 g / cm ³ , more preferably 2.25 to 2.60 g / cm ³ . When the carrier is porous, or the surface irregularities are large and the bulk density is less than 2.15, the substantial magnetization per particle is increased even if the amount of magnetization (emu / g) of 1 KOe of the core particle is large. Since the value is small, it is disadvantageous for carrier adhesion.

To increase the bulk density, it is possible to increase the firing temperature. However, it is preferable that the core particles are less than 2.7 g / cm ³ because the core particles are easily fused and difficult to disintegrate. More preferably, it is less than 6 g / cm ³ .

According to the metal powder-apparent density test method (JIS-Z-2504), the carrier according to the present invention has a bulk density of 25 cm ³ made of stainless steel, which is allowed to flow naturally from an orifice having a diameter of 2.5 mm. After pouring the carrier into the cylindrical container until it overflows, the upper surface of the container is scraped flat with a single operation along the upper end of the container using a nonmagnetic horizontal spatula. If it is difficult to flow with an orifice having a diameter of 2.5 mm, the carrier naturally flows out from the orifice having a diameter of 5 mm. By this operation, the weight of the carrier per cm ^{3 is} obtained by dividing the weight of the carrier flowing into the container by the volume of the container 25 cm ³ . This is defined as the bulk density of the carrier.
It is also effective to use the carrier described above and the toner of the present invention as a developer.

(Image forming device)
The image forming apparatus of the present invention includes an electrostatic latent image forming process (charging process and exposure process), a developing process, a transfer process, and a fixing process, and if necessary, a charge eliminating process, a cleaning process, and a recycling process. You may further have processes, such as a process and a control process.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming unit preferably has a charger (charging unit) that uniformly charges the surface of the image carrier and an exposure unit (exposure unit) that exposes the surface of the image carrier.

Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.
The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the toner of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing unit that accommodates the toner of the present invention and can apply the toner to the electrostatic latent image in a contact or non-contact manner. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used.

  In the developing device, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and is held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

  The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.

The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.
The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used. It is preferable to use a blade cleaner.

  The recycling process is a process in which the toner removed in the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.

  A control process is a process of controlling each process, and can be performed using a control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  The process cartridge of the present invention is used in the image forming apparatus of the present invention, and integrally supports an image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit to form the image of the present invention. It is detachable from the main body.

  FIG. 2 shows an example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a drum-shaped photosensitive member 10 as an image carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member 50. And a cleaning device 60 as a cleaning means and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is stretched by three rollers 51 so as to be movable in the direction of the arrow. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording sheet 95 serving as a recording medium is disposed to face the recording paper 95. . Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. The black developing device 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developer roller 44M. The cyan developer 45C includes a developer container 42C, the developer supply roller 43C, and a developer. A roller 44C is provided. The developing belt 41 is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part of the developing belt 41 is in contact with the photoreceptor 10.

  In the image forming apparatus 100A, the charging roller 20 charges the photoreceptor 10 uniformly, and then exposes the photoreceptor 10 using the exposure apparatus 30 to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoreceptor 10 is developed by supplying a developer from the developing device 40 to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied by the roller 51, and further transferred (secondary transfer) onto the recording paper 95. As a result, a transfer image is formed on the recording paper 95. The toner remaining on the photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, and the charged charge on the photoconductor 10 is removed by a static elimination lamp 70.

  FIG. 3 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not include the developing belt 41, except that a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged around the photoconductor 10 so as to face each other. It has the same configuration as that of the image forming apparatus 100A and exhibits the same function and effect.

FIG. 4 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16 so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support rollers 14 and 15 is provided with a tandem developing device in which image forming means 18 of four colors of yellow, cyan, magenta, and black are opposed to each other along the conveying direction. 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It is. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Thereby, images can be formed on both sides of the recording paper.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. First, a document is set on the document table 130 of the automatic document feeder 400, or the automatic document feeder 400 is opened to set a document on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.

  When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed onto the contact glass 32, on the other hand, when an original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body 33 is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means 18 of each color in the tandem developing device 120, and a toner image of each color is formed.

  The toner image on the black photoconductor 10K, the toner image on the yellow photoconductor 10Y, the toner image on the magenta photoconductor 10M, and the toner image on the cyan photoconductor 10C are sequentially transferred onto the intermediate transfer member 50. (Primary transfer). Then, the toner images of the respective colors are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  As shown in FIG. 5, the image forming means 18 for each color in the tandem developing device 120 is a photoconductor 10, a charger 59 for uniformly charging the photoconductor 10, and the image information for each color. By exposing the body 10 (L in the figure), an exposure device 21 that forms an electrostatic latent image on the photoreceptor 10, and developing the electrostatic latent image using toner of each color, the photoreceptor 10 A developing unit 61 that forms toner images of the respective colors, a transfer charger 62 that transfers the toner images of the respective colors onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64 are provided.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142a is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145a. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142b is rotated to feed out the recording paper on the manual feed tray 52, separated one by one by the separation roller 145b, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller 49 is rotated in time with the color transfer image formed on the intermediate transfer member 50, and the recording paper is fed between the intermediate transfer member 50 and the secondary transfer device 22, thereby being recorded on the recording paper. A color transfer image is formed. The toner remaining on the intermediate transfer member 50 after the transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording paper on which the color transfer image is formed is conveyed to the fixing device 25 by the secondary transfer device 22, and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  According to the present invention, an image can be formed at a speed of 55 sheets / min or more when an image is formed on the A4 size recording medium with the recording medium feeding direction as the short direction of the recording medium. An apparatus can be provided.

[Toner characteristics measurement method]
<Weight average particle diameter (Dw), volume average particle diameter (Dv), and number average particle diameter (Dn)>
The weight average particle diameter (Dw), volume average particle diameter (Dv), and number average particle diameter (Dn) of the toner were measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. It can be measured and analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). As a specific example, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and 0.5 g of each toner is added. The mixture was stirred, and then 80 ml of ion exchange water was added. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

  The ratio (Dw / Dn) of the weight average particle diameter (Dw) to the number average particle diameter (Dn) in the toner manufactured by the manufacturing method of the present invention is preferably 1.29 or less. When Dw / Dn exceeds 1.30, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. is there.

  Further, when the ratio of the weight average particle diameter to the number average particle diameter (Dw / Dn) of the toner is 1.00 to 1.29, any of storage stability, low-temperature fixability, and hot offset resistance can be obtained. Also tends to be an excellent toner. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. In the two-component developer, even if the toner balance is performed for a long period of time, the toner particle diameter in the developer does not fluctuate, and good and stable developability can be obtained even with long-term stirring in the developing device. In addition, in the case of a one-component developer, fluctuations in the toner particle diameter are reduced even when the balance of toner is performed, and toner filming on the developing roller and the toner on the member such as a blade for thinning the toner There is no fusion and good and stable developability can be obtained even when the developing device is used for a long time (stirring). Therefore, according to the present invention, a high-quality image can be obtained.

<Average circularity>
The average circularity of the toner is defined by the average circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. Measurement can be performed using a flow particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation), and analysis can be performed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). As a specific example, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 Add 0.5 g and stir with microspatel, then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). For the dispersion, the shape and distribution of the toner are measured using the FPIA-2100 until a density of 5,000 to 15,000 / μl is obtained.

  In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μl from the viewpoint of measurement reproducibility of average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

<Acid value>
In the present invention, the acid value can be measured using a method based on JIS K0070-1992.
As a specific example, first, 0.5 g of a sample (0.3 g in the case where ethyl acetate is soluble) is added to 120 ml of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 ml of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, the acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000.
For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used. At this time, the measurement conditions are the same as in the case of the hydroxyl value.
The acid value can be measured as described above. Specifically, the acid value is titrated with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and from the titration, the formula acid value [KOHmg / g] = Titrate [ml] x N x 56.1 [mg / ml] / sample weight [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

The acid value of the toner of the present invention is an important index for low-temperature fixability and high-temperature offset resistance, and is derived from the terminal carboxyl group of the unmodified polyester resin. In order to control the offset generation temperature and the like, it is preferably 0.5 to 40 KOH mg / g.
When the acid value exceeds 40 KOH mg / g, the extension reaction and / or the crosslinking reaction of the reactive modified polyester resin may be insufficient, and the high temperature offset resistance may be lowered. On the other hand, if the acid value is less than 0.5 KOHmg / g, the effect of improving the dispersion stability by the base at the time of production cannot be obtained, or the elongation reaction and / or the crosslinking reaction of the reactive modified polyester resin can easily proceed. As a result, the production stability may be reduced.

<Glass transition temperature>
In the present invention, the polyester resin preferably has a glass transition point of 40 to 70 ° C. When the glass transition point is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
In the present invention, the glass transition point can be measured using Rigaku THRMOFLEX TG8110 (Rigaku Corporation) and 10TG-DSC system TAS-100 (Rigaku Corporation).
Specifically, first, an aluminum sample container containing about 10 mg of sample is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is allowed to stand at 150 ° C. for 10 minutes. The DSC measurement is performed by heating at a rate of 10 ° C./min.
The glass transition point is calculated from the tangent line of the endothermic curve near the glass transition point and the base line using the analysis system in the TAS-100 system.

(1 component developer, 2 component developer)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, and polyamide resin.

  Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins, epoxy resins, and the like.

Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example and comparative example which are illustrated here. In addition, the part in an Example represents a mass part unless there is particular description.

<Example 1>
Manufacture of toner 1 (preparation of solution or dispersion of toner material)
~ Synthesis of unmodified polyester (low molecular weight polyester) ~
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of masterbatch (MB)-
1000 parts by mass of water, 540 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Preparation of toner material phase 1-
In a beaker, 100 parts by mass of the unmodified polyester and 130 parts by mass of ethyl acetate were stirred and dissolved. Next, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)), 10 parts by mass of the masterbatch, and a layered inorganic mineral as a charge control agent Organic cation-modified clay (Craytone Apa manufactured by SCP Co., Ltd .: montmorillonite layered mineral ion-exchanged with quaternary ammonium ions (cations)), 0.5 parts by mass 3 passes using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.) under the condition that the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and 0.5 mm zirconia beads are filled by 80% by volume. A raw material solution was prepared to prepare a toner material solution or dispersion.

(Preparation of resin fine particles 1)
In a reaction vessel in which a stir bar and a thermometer were set, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion 1] was obtained. The volume average particle size of the [resin fine particle dispersion 1] (measured with LA-920 manufactured by Horiba, Ltd.) was 9 nm.

-Preparation of aqueous medium phase-
660 parts by mass of water, 25 parts by mass of the above [resin fine particle dispersion 1], 25 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 60 parts by mass were mixed and stirred to obtain a milky white liquid (aqueous medium phase).

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

~ Removal of organic solvent ~
100 parts by mass of the emulsified slurry was charged into a flask equipped with a degassing pipe, a stirrer, and a thermometer, and the solvent was removed under reduced pressure at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min. It was.

~Washing~
After filtering the entire amount of the solvent removal slurry A under reduced pressure, 300 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer, redispersed (at 12,000 rpm for 10 minutes) and then filtered. . To the obtained filter cake, 300 parts by mass of ion-exchanged water was added and mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered three times.

~ Heat treatment ~
The resulting washed slurry was aged at 45 ° C. for 10 hours, filtered and a heat-treated cake was obtained.

~ Dry ~
After the heat treatment, the cake was dried at 45 ° C. for 48 hours in a forward air dryer, and sieved with a mesh having an opening of 75 μm, whereby toner base particles 1 were obtained.

~ Preparation of external additives ~
In a 3 liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 693.0 parts by mass of methanol, 46.0 parts by mass of water, and 55.3 parts by mass of 28% ammonium tetramethoic water were added and mixed. . While this solution was adjusted to 42 ° C. and stirred, 1293.0 parts by mass (8.5 mol) of silane and 464.5 parts by mass of 5.4% aqueous ammonia were started simultaneously, the former being 6 hours and the latter being 4 It was added dropwise over time.
After the tetramethoxysilane was added dropwise, stirring was continued for 0.5 hour to effect hydrolysis to obtain a silica fine particle suspension. To the obtained suspension, 547.4 parts by mass (3.39 mol) of hexamethyldisilazane was added at room temperature, heated to 120 ° C. and reacted for 3 hours to trimethylsilylate the silica fine particles.
Thereafter, the solvent was distilled off under reduced pressure to obtain 553.0 parts by mass of silica having an average primary particle size of 80 nm. In the production of the fused silica, fused silica (additive 1) having an average secondary particle size of 160 nm, which was secondarily aggregated with various treatment agents using silica primary particles having various average particle sizes, was produced. The degree of coalescence was adjusted according to the average particle diameter of the silica primary particles used, the treatment agent, the mixing ratio of the silica primary particles and the treatment agent, and the treatment conditions (firing temperature, firing time). Mixing of the silica primary particles and the treating agent was performed using a spray dryer.

~ Additive mixing ~
H1303 (average primary particle size 23 nm, Clariant Japan) formed with 2.5 parts of non-spherical silica produced by a sol-gel method formed with secondary particles on 100 parts of toner base particles 1 as additive 1 and primary particles 0.6 part) was added, and 0.5 part of hydrophobized titanium oxide formed by primary particles was mixed with a Henschel mixer to obtain toner 1.
Formula (i) showing the relationship between the amount of layered inorganic mineral (A) in the charge control agent of toner 1 and inorganic particles (B) in additive 1 is B / A = 6.3.

Table 1 shows the ratio of B / A in Examples and Comparative Examples. In Table 1, “charge amount” indicates the amount of the layered inorganic mineral (charge control agent) added in the step of adjusting the toner material phase 1, and “actual amount” indicates the toner base particle 1 The amount of the above-mentioned layered inorganic mineral (charge control agent) relative to 100 parts of is shown. The “actual amount” is obtained as the amount of the layered inorganic mineral (charge control agent) with respect to 100 parts of the solid content in the toner material phase 1.
In Example 1, Nx = 200 in formula (ii) and Db50 / Db10 = 1.15 in formula (iii).

<Example 2>
Toner 2 was obtained in the same manner as in Example 1 except that Additive 1 was changed to 2.7 parts and B / A = 6.8 in the production process in Example 1.

<Example 3>
In the production process of Example 1, the toner 3 was prepared in the same manner as in Example 1 except that the charge control agent was changed to 1.5 parts, the additive 1 was changed to 1.7 parts, and B / A = 1.4. Obtained.

<Example 4>
Toner 4 was prepared in the same manner as in Example 1 except that the charge control agent was changed to 1.5 parts, additive 1 was changed to 2.2 parts, and B / A = 1.8 in the production process in Example 1. Obtained.

<Example 5>
Toner 5 was prepared in the same manner as in Example 1 except that the charge control agent was changed to 1.5 parts, additive 1 was changed to 2.1 parts, and B / A = 1.8 in the production process in Example 1. Obtained.

<Example 6>
Toner 6 was prepared in the same manner as in Example 1 except that the charge control agent was changed to 0.5 part, additive 1 was changed to 2.2 parts, and B / A = 5.5 in the production process in Example 1. Obtained.

<Example 7>
In the production process of Example 1, the toner 7 was changed in the same manner as in Example 1 except that the charge control agent was changed to 0.5 part, the additive 1 was changed to 2.3 parts, and B / A = 5.8. Obtained.

<Example 8>
Implementation was performed except that additive 1 in the production process in Example 1 was changed to UFP-35H (manufactured by Electrochemical Co., Ltd., average particle diameter of 150 nm) as a additive based on secondary particles formed by fusion bonding as additive 2. In the same manner as in Example 1, Toner 8 was obtained. B / A at this time is 6.3.
The average primary particle size of UFP-35H is 78 nm. However, since the secondary primary particle-shaped non-spherical insulating inorganic particles in which a plurality of primary particles of Example 1 are combined are used, the average particle size is as described above. 150 nm.

<Example 9>
Toner 9 was obtained in the same manner as in Example 4 except that Additive 1 in the production process in Example 4 was changed to Additive 2. At this time, B / A = 1.8.

<Example 10>
Toner 10 was obtained in the same manner as in Example 1 except that Additive 1 in the production process in Example 1 was changed to the additive in formula (ii) where Nx = 300. B / A at this time is 6.3.
In addition, about the said additive, Nx was controlled by adjusting a calcination temperature. The same shall apply hereinafter.

<Example 11>
Toner 11 was obtained in the same manner as in Example 4 except that Additive 1 in the production process in Example 4 was changed to an additive in formula (ii) where Nx = 300. At this time, B / A = 1.8.

<Example 12>
A toner 12 was obtained in the same manner as in Example 1 except that the additive 1 in the production process in Example 1 was changed to the additive in formula (ii) where Nx = 200. B / A at this time is 6.3.

<Example 13>
Toner 13 was obtained in the same manner as in Example 4 except that Additive 1 in the production process of Example 4 was changed to the additive of formula (ii) where Nx = 200. At this time, B / A = 1.8.

<Example 14>
Toner 14 was obtained in the same manner as in Example 1 except that Additive 1 in the production process in Example 1 was changed to the additive of Db50 / Db10 = 1.20 in formula (iii). B / A at this time is 6.3.
In addition, about the said additive, Db50 / Db10 was controlled by performing a classification process with a classifier. The same shall apply hereinafter.

<Example 15>
Toner 15 was obtained in the same manner as in Example 4 except that Additive 1 in the production process in Example 4 was changed to an additive of Db50 / Db10 = 1.20 in formula (iii). At this time, B / A = 1.8.

<Example 16>
Toner 16 was obtained in the same manner as in Example 1 except that Additive 1 in the production process in Example 1 was changed to the additive of Db50 / Db10 = 1.15 in formula (iii). B / A at this time is 6.3.

<Example 17>
Toner 17 was obtained in the same manner as in Example 4 except that Additive 1 in the production process in Example 4 was changed to an additive of Db50 / Db10 = 1.15 in formula (iii). At this time, B / A = 1.8.

<Example 18>
For additive 1 in the production process of Example 1, toner 18 was obtained in the same manner as in Example 1 except that the average secondary particle diameter Db was changed to 80 nm. B / A at this time is 6.3.

<Example 19>
For additive 1 in the production process of Example 4, toner 19 was obtained in the same manner as in Example 4 except that the average secondary particle diameter Db was changed to 80 nm. At this time, B / A = 1.8.

<Example 20>
For additive 1 in the production process of Example 1, toner 20 was obtained in the same manner as in Example 1 except that the average secondary particle diameter Db was changed to 200 nm. B / A at this time is 6.3.

<Example 21>
For additive 1 in the production process of Example 4, toner 21 was obtained in the same manner as in Example 4 except that the average secondary particle diameter Db was changed to 200 nm. At this time, B / A = 1.8.

<Example 22>
~ Synthesis of crystalline polyester resin ~
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,300 g of 1,6-alkanediol, 2530 g of fumaric acid, 291 g of trimellitic anhydride, and 4.9 g of hydroquinone were added. After reacting at 5 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain [Crystalline Polyester Resin 1].

~ Preparation of crystalline polyester dispersion ~
100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice water bath at a rate of 27 ° C./min. To this, 500 ml of glass beads (3 mmφ) was added, and pulverized for 10 hours with a batch type sand mill (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion 1].

-Preparation of toner material phase 2-
In a beaker, 100 parts by mass of the unmodified polyester and 130 parts by mass of ethyl acetate were stirred and dissolved. Next, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)), 10 parts by mass of the master batch, and inorganic layered mineral as a charge control agent Organic cation-modified clay (Craytone Apa manufactured by SCP Co., Ltd .: montmorillonite layered mineral ion-exchanged with quaternary ammonium ions (cations)), 0.5 mass part 10 parts by weight of the above-mentioned [Crystalline Polyester Dispersion 1] was added as a solid content, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 3 passes under the condition that 80% by volume of 0.5 mm zirconia beads are filled to prepare a raw material solution and dissolve the toner material. A dispersion was prepared.
Other steps were carried out in the same manner as in Example 1 to obtain toner 22. B / A at this time is 6.3.

<Example 23>
In the production process of Example 4, a crystalline polyester was added in the same manner as in Example 22 to obtain Toner 23. B / A at this time is 2.0.

<Comparative Example 1>
In the production process of Example 1, the toner 24 was changed in the same manner as in Example 1 except that the charge control agent was changed to 0.5 part, the additive 1 was changed to 3.0 parts, and B / A = 7.2. Obtained.

<Comparative example 2>
In the production process of Example 1, the toner 25 was changed in the same manner as in Example 1 except that the charge control agent was changed to 0.5 part, the additive 1 was changed to 3.2 parts, and B / A = 7.7. Obtained.

<Comparative Example 3>
In the production process of Example 1, the toner 26 was changed in the same manner as in Example 1 except that the charge control agent was changed to 2.0 parts, the additive 1 was changed to 2.0 parts, and B / A = 1.2. Obtained.

<Comparative example 4>
In the production process of Example 1, the toner 27 was changed in the same manner as in Example 1 except that the charge control agent was changed to 2.0 parts, the additive 1 was changed to 1.5 parts, and B / A = 0.9. Obtained.

<Comparative Example 5>
Toner 28 was obtained in the same manner as in Example 4 except that additive 1 in the production process in Example 4 was changed to additive 3 as alumina oxide fine powder (Aluminium Oxide C, manufactured by Aerosil).

<Comparative Example 6>
For additive 1 in the production process in Example 4, toner 29 was obtained in the same manner as in Example 4 using titanium oxide powder (JMT-150IB, manufactured by Teika Co., Ltd.) as additive 4.

<Comparative Example 7>
The toner in the same manner as in Example 4 except that the additive 1 in the production process in Example 4 was changed to UFP-35 (manufactured by Electrochemical Co., Ltd., average particle diameter: 78 nm) as the additive 5 by a dry process. 30 was obtained.

<Comparative Example 8>
Example 4 is the same as Example 4 except that additive 1 in the production process in Example 4 is changed to X24 (average particle size 170 nm, manufactured by Shin-Etsu Chemical Co., Ltd.) of sol-gel spherical silica formed with primary particles as additive 6. Similarly, a toner 31 was obtained.

  Table 1 shows the values of B / A in Examples and Comparative Examples.

[Creation of carrier]
Next, a specific example of manufacturing the carrier used for the actual toner evaluation will be described. The carrier used in the present invention is not limited to these examples.
~ Career ~
Acrylic resin solution (solid content 50 wt%) 21.0 parts Guanamin solution (solid content 70 wt%) 6.4 parts Alumina particles [0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts Silicone resin solution 65 0.0 part [solid content 23 wt% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part [Solid content 100 wt% (SH6020: manufactured by Toray Dow Corning Silicone)]
Toluene 60.0 parts Butyl cellosolve 60.0 parts

The carrier raw material was dispersed with a homomixer for 10 minutes to obtain a coating film forming solution of an acrylic resin and a silicone resin containing alumina particles. Firing ferrite powder [(MgO) 1.8 (MnO) 49.5 (Fe ₂ O ₃ ) 48.0: average particle size; 25 μm] as the core material is coated with the above coating film forming solution on the surface of the core material. The coated ferrite powder was obtained by applying with a Spira coater (Okada Seiko Co., Ltd.) to a thickness of 15 μm and drying. The obtained coated ferrite powder was fired in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, a carrier a having a weight average particle diameter of 35 μm was obtained.

[Preparation of two-component developer]
Using the toners 1 to 31 and the carrier a described above, 7 parts by mass of toner with respect to 100 parts by mass of the carrier are uniformly mixed and charged using a type of tumbler mixer in which the container rolls and stirs, and two-component development is performed. Agents 1-31 were produced.

[Evaluation of toner]
Each evaluation was performed using a digital full-color copying machine (image MP MP6000 manufactured by Ricoh).

(Liquidity)
The fluidity was judged by the degree of toner aggregation. The degree of toner aggregation is an index representing the adhesive force between toners. If the value is large, the adhesive force between toners is large, and the development flyability deteriorates. To measure the degree of toner aggregation, a powder tester (manufactured by Hosokawa Micron Corporation) is used, and sieves with openings of 75 μm, 45 μm and 22 μm are arranged in this order from above. The vibration was applied for 30 seconds, the toner weight on each sieve was measured after the vibration, and the weights of 0.5, 0.3 and 0.1 were respectively added and calculated as a percentage.
〔Evaluation criteria〕
◎: 14% or less ○: 15-18%
Δ: 19-22%
X: 23% or more

(Chargeability)
In a room temperature and humidity room (temperature 23.5 ° C., humidity 60% RH), the humidity is adjusted for 30 minutes or more in an open system. After adding 6.000 g of initial carrier and 0.452 g of toner to a stainless steel container, the container is sealed. The sample, which was run on a scale 150 with a YS-LD (a shaker manufactured by Yayoi Co., Ltd.) for 1 minute and was triboelectrically charged with an amplitude of about 1100 times, was subjected to a general blow-off method [Toshiba Chemical Co., Ltd. Manufactured by TB-200].
〔Evaluation criteria〕
Hereinafter, the unit is (−μc / g).
◎: Greater than 30 and less than 35 ○: Greater than 25 and less than or equal to 35 and less than 40 △: Greater than 20 and less than 25 or 40 and less than 45

(Transfer stability)
After the image area ratio 20% chart is transferred from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before the cleaning is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.). Measured and evaluated according to the following criteria.
〔Evaluation criteria〕
A: The difference from the blank is less than 0.005.
(Circle): The difference with a blank is 0.005-0.010.
(Triangle | delta): The difference with a blank is 0.011-0.020.
X: The difference with a blank exceeds 0.02.

(Filming property)
Filming on the developing roller after the output of 1000 band charts having an image area ratio of 100%, 75%, and 50% and filming on the photoreceptor were observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: Filming does not occur at all.
○: The occurrence of filming can be confirmed slightly.
Δ: Filming occurs in streaks.
X: Filming has occurred on the entire surface.

Table 2 summarizes the evaluation results of the developers 1 to 31 using the toners 1 to 31 produced in Examples 1 to 23 and Comparative Examples 1 to 8.

  It has been clarified that the toner within the scope of the present invention is a toner excellent in fluidity, chargeability, transfer stability, and filming resistance.

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer Device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing Belt 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developer roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan Present Device 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 59 Charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording paper 100A, 100B, 100C Image forming device 110 Belt type fixing device 120 Tandem type developer 130 Document table 142a, 142b Paper feed roller 143 Paper bank 144 Paper feed cassette 145a, 145b Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copier main body 200 Feeding table 300 Scanner 400 Automatic document feeder

JP 2009-098194 A JP 2010-224502 A JP 2011-027791 A Japanese Patent No. 2837678

Claims (10)

An electrostatic charge image developing toner comprising an external additive attached to the surface of a toner containing a binder resin, a colorant, a release agent, and a charge control agent,
The charge control agent includes a layered inorganic mineral in which interlayer ions are modified with organic ions,
The external additive includes non-spherical insulating inorganic particles in a secondary particle shape in which a plurality of primary particles are coalesced,
A toner for developing an electrostatic charge image, wherein the relationship between the weight% (A) of the layered inorganic mineral and the weight% (B) of the non-spherical insulating inorganic particles satisfies the following formula (i).
1.3 <B / A <7.0 Formula (i)   The electrostatic image developing toner according to claim 1, wherein the non-spherical insulating inorganic particles are silica prepared by a sol-gel method.   3. The electrostatic image developing toner according to claim 1, wherein the range of the formula (i) is 1.7 <B / A <6.4. The electrostatic image developing toner according to claim 1, wherein the non-spherical insulating inorganic particles satisfy the following formula (ii).
Nx / 1000 × 100 ≦ 30 [%] Formula (ii)
[In the formula (ii), Nx represents the number of cracked or disintegrated particles in 1,000 of the non-spherical insulating inorganic particles. ] 5. The electrostatic image developing toner according to claim 1, wherein the non-spherical insulating inorganic particles satisfy the following formula (iii): 6.
Db50 / Db10 ≦ 1.20 Formula (iii)
[However, in the above formula (iii), the average particle diameter of the 50th% measured from the small particle side of the secondary particle diameter Db observed by the FE-SEM is Db50, the 10th% measured from the small particle side. The average particle diameter of Db10 is taken as Db10. ]   6. The electrostatic image developing toner according to claim 1, wherein the non-spherical insulating inorganic particles have an average secondary particle diameter Db in the range of 80 nm to 200 nm.   7. The electrostatic image developing toner according to claim 1, wherein the binder resin contains a crystalline resin and an amorphous resin.   A developer comprising a carrier and the toner according to claim 1.   An electrostatic latent image carrier, an electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image carrier, and a toner for developing the electrostatic latent image to form a visible image A developing step, a transfer step of transferring the visible image on the electrostatic latent image carrier onto a recording medium, and a fixing step of fixing the transferred image transferred onto the recording medium, An image forming apparatus, wherein the toner is the toner according to claim 1.   The image can be formed at a speed of 55 sheets / min or more when an image is formed on the recording medium of A4 size with the feeding direction of the recording medium as the short direction of the recording medium. The image forming apparatus according to claim 9.