JP4857154B2 - Aggregated toner - Google Patents

Description

  The present invention relates to a toner particle used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method. In particular, it relates to an agglomerated toner.

  In the conventional electrophotographic method, after charging on a photosensitive drum by various means, an electric latent image is formed, then toner is developed on the latent image, and the toner image is transferred onto a transfer material such as paper. Furthermore, the toner image is obtained by fixing by means such as heating and pressurization (see, for example, Non-Patent Document 1).

  In recent years, in printers and copiers based on the above method, there is an increasing demand for images that are the same as the initial images even when printed over a long period of time and environmental support, and high image quality, high reliability, and environmental support are indispensable for machine design. It has become a thing.

  Here, high image quality and high reliability indicate that even if printing is performed over a long period of time, a level that is the same as the initial print image is continuously output. More specifically, the transfer uniformity is excellent even on transfer papers having different transfer states, and there is little contamination on the member that greatly affects the quality of the output image, and an excellent image is continuously output.

  Environment-friendly means that the amount of waste toner is small and that a printed image is output with low power consumption. Specifically, good transfer efficiency and good low-temperature fixability can be obtained.

  In response to this need, expectations are high for a toner production method using an agglomeration method due to the wide selection of materials that improve the fixing characteristics over conventional pulverization methods and the variety of toner structures.

  For the purpose of ensuring excellent gloss, a proposal specifying the weight average molecular weight Mw and peak molecular weight Mp of the binder, the weight average molecular weight Mw and peak molecular weight Mp of the toner particles, the molecular weight distribution MWD, the average roundness and the cohesiveness is proposed. Yes (see, for example, Patent Document 1).

  Specifically, in the agglomerated toner, the styrene-acrylate binder is Mw (about 20 to about 30 kpse) and Mp (about 23 to about 28 kpse), the toner particles are Mw (about 28 to about 130 kpse), Mp (about 9 to about 30 kpse). 13.4 kpse), MWD (molecular weight distribution of about 2.2 to about 10), average roundness (about 0.94 to about 0.98), cohesiveness (about 55 to about 98%). .

  However, the patent document does not disclose the present case because the description regarding the transfer uniformity of the effect and the contamination resistance of the member is not sufficient.

  For the purpose of ensuring good color reproducibility, high transparency, high glossiness, spent resistance, etc., the dispersion state of release agent particles and the amount of inorganic fine powders with two average particle sizes are specified in agglomerated toner (For example, refer to Patent Document 2).

  Specifically, in the aggregated toner, the 16% diameter (PR16) of the volume particle size cumulative distribution is 20 to 200 nm, the 50% diameter (PR50) is 40 to 300 nm, the 84% diameter (PR84) is 400 nm or less, and PR84 / PR16. A release agent particle having a particle diameter of 1.2 to 2.0 is dispersed. An inorganic fine powder having an average particle size of 6 to 20 nm is 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the toner base, and an inorganic fine powder having an average particle size of 20 to 200 nm is 1. 0 to 3.5 parts by mass.

  However, in the above-mentioned patent document, there is no sufficient logical development in the description relating to achieving both the low-temperature fixability and transferability of the present effect. In addition, there is no description in the examples about non-magnetic one-component development. Therefore, this case is not disclosed.

  There is a proposal to use two types of hydrophobic silica in combination with one type of hydrophobic titanium oxide for the purpose of ensuring charging stability, transferability at the time of pressure transfer, and excellent chargeability even without a charge control agent (for example, patents) Reference 3).

  Specifically, a first hydrophobic silica having an average primary particle size of 5 to 18 nm and a second hydrophobic silica having an average primary particle size of 18 to 50 nm and an average primary particle size larger than the first hydrophobic silica. And a hydrophobic titanium oxide having an average primary particle size of 10 to 40 nm.

  However, the above-mentioned patent document does not disclose the present case because there is no sufficient logical development in the description relating to achieving both the low-temperature fixability and the transferability of the present effect.

JP 2005-182063 A JP 2005-31506 A JP 2003-202702 A The Electrophotographic Society "Basics and Applications of Electrophotographic Technology" Corona Co., Ltd. June 15, 1988, P46-79

  The problem to be solved by the present invention is to solve the improvement of the low-temperature fixability, the improvement of the transfer efficiency, the improvement of the transfer uniformity, and the improvement of the stain resistance.

  An object of the first invention according to the present invention is to solve the improvement in low-temperature fixability, the improvement in transfer efficiency, the improvement in transfer uniformity, and the improvement in resistance to member contamination.

  The object of the second invention according to the present invention is to solve the improvement in transfer efficiency and the transfer uniformity.

  An object of the third invention according to the present invention is to solve an improvement in transfer efficiency.

  An object of the fourth invention according to the present invention is to solve the improvement of the transfer efficiency and the transfer uniformity.

  An object of the fifth invention according to the present invention is to solve, in particular, improvement in low-temperature fixability, improvement in transfer uniformity, and improvement in resistance to member contamination.

  An object of the sixth aspect of the present invention is to solve the improvement of transfer efficiency and transfer uniformity.

  An object of the seventh invention of the present invention is to solve, in particular, improvement of transfer efficiency, improvement of transfer uniformity, and improvement of resistance to member contamination.

  An object of the eighth invention according to the present invention is to solve the improvement in the resistance to member contamination.

In order to achieve the above object, a first invention according to the present application provides a toner obtained through a step of aggregating at least polymer fine particles and colorant fine particles to obtain an agglomerate and a step of aging the agglomerate. An agglomerated toner having particles,
The aggregated toner may have a titanium oxide primary particle here the number average particle diameter of 80 to 300nm silica primary particles here the number average particle size of 10 to 100 nm,
The toner has a THF-soluble peak molecular weight of 10,000 to 35,000, the toner has a specific surface area of 2.00 to 7.00 m ² / g, and the toner has a Si / Ti intensity ratio of 4.5 to 22.0.

  The second invention according to the present application is characterized in that in the aggregation toner, the polymer fine particles are vinyl polymer fine particles produced by an emulsion polymerization method.

  A third invention according to the present application is an aggregated toner, wherein the average circularity of the toner is 0.950 to 0.980.

A fourth invention according to the present application is characterized in that, in the aggregated toner, the bromine content of the toner is 200 to 1200 ppm.

  According to the present invention, in the aggregated toner obtained by adhering the inorganic fine powder to the toner particles obtained by the aggregation method including the aggregation step and the aging step, at least the polymer fine particles and the colorant fine particles, Kind of inorganic fine powder, number average particle diameter of inorganic fine powder, total amount of inorganic fine powder with respect to toner, peak molecular weight of toner THF soluble content, specific surface area of toner, average circularity of toner, bromine content of toner, By combining the silicon / titanium ratio of the toner and the weight average particle diameter / number average particle diameter ratio of the toner, all of the above-mentioned problems, such as low-temperature fixability, transfer efficiency, transfer uniformity, and member contamination resistance, are all achieved. Can be provided.

  Moreover, even if it uses for the contact one-component developing method, the said effect can be expressed effectively.

  The toner and the image forming method as described in the above patent document satisfy all of the low-temperature fixability, high transfer efficiency, transfer uniformity, and member contamination resistance simultaneously for users who require high-quality images. However, it seems that the effect is not necessarily expected.

  In order to obtain excellent low-temperature fixability, the inventors have reduced the molecular weight of the polymer fine particles, reduced the peak molecular weight of the polymer fine particles, reduced the melt viscosity, I thought it was important to increase the sex.

  Among these, attention was focused on reducing the peak molecular weight of the polymer fine particles that dominate the outermost layer of the toner and decreasing the melt viscosity. Although there are various methods for achieving the above-mentioned point of view, it was considered important to produce polymer fine particles using a chain transfer agent in order to achieve the best effects of the present invention. Then, after the resin was polymerized with the optimum addition amount of the chain transfer agent, it was present in the outermost surface layer of the toner in the aggregation process and the aging process. By doing this, it was possible to fix the toner particles and the material material (so-called transfer paper) with a small amount of heat, and the low-temperature fixability that satisfied the present case was derived.

  Next, explanation will be given for obtaining excellent transfer efficiency.

  In order to achieve excellent transfer efficiency, the present inventors have promoted the spheroidization of the toner, and suppressed the state change as much as possible even when the inorganic fine powder adhered to the toner particle surface is printed over a long period of time. Therefore, it was considered important to make the charging characteristics of the toner surface more uniform.

  In order to achieve the above-mentioned point of view, toner spheroidization was promoted by adjusting the production conditions (temperature / number of revolutions / aggregation time / aging time, etc.) of the aggregation process and the aging process. Further, silica having a primary particle number average particle diameter within the suitability range of the present invention was allowed to exist on the surface of the aggregated toner. By doing so, it was possible to efficiently transmit a small current and pressure during transfer to the toner, and the transfer efficiency that satisfied the present case was derived.

  Next, explanation will be given for obtaining excellent transfer uniformity.

  The present inventors considered that it is important to make the charging characteristics of the toner surface more uniform in order to obtain excellent transfer uniformity.

  In order to achieve the above-mentioned point of focus, in addition to performing the same thing that expresses high transfer efficiency, in addition, in order to maintain the initial image even after long-term printing, the above-described silica and oxide are oxidized on the surface of the aggregated toner. Titanium was present in a uniform state. In this way, even when printing for a long period of time, it is possible to efficiently transmit a small current and pressure at the time of transfer to each toner, and the transfer uniformity satisfying the present case is derived.

  Next, an explanation will be given for obtaining excellent component contamination resistance.

  In order to obtain excellent member contamination resistance, the present inventors consider that it is important not to release inorganic fine powder adhering to the toner particle surface, or to select a material that is difficult to contaminate. It was.

  In order to achieve the above-mentioned attention point, it was necessary that the silica and titanium oxide were present on the surface of the aggregated toner so that the strength ratio was within the suitability range of the present case. By doing so, it was considered that the inorganic fine powder which is easily contaminated becomes difficult to be liberated even after long-term printing, and the satisfactory stain resistance of the member can be derived.

  The present invention proposes to satisfy all of the above-mentioned problems of low-temperature fixability, transfer efficiency, transfer uniformity, and resistance to member contamination at the same time. For this purpose, the bromine content in the toner is optimized. I think that is the most important. The estimation mechanism is described below.

The amount of bromine here is due to the chain transfer agent. Controlling the peak molecular weight of polymer fine particles using a chain transfer agent also leads to sharpening of the molecular weight distribution. In the case of the configuration in which polymer fine particles are arranged on the toner surface as in the present invention, the above sharpening results in the sharpening of the molecular weight distribution of the toner surface layer, suggesting that the surface composition of the toner of the present invention is uniform. is doing. Since the toner particles have a uniform surface composition, the silica and titanium oxide of the present invention can be uniformly attached. As a result, toner particles considering low-temperature fixability are generally fragile to external heat and frictional forces.
Although it is difficult to achieve both developability and transferability, it is considered that the present invention can satisfy the four effects of the present invention at the same time because there is a certain uniform layer.

  Furthermore, the most preferred chain transfer agent used in the present invention is an organic halogen compound. Among these, those using bromine are preferable. Since bromine has a high electronegativity, it has an electron withdrawing property. Therefore, when bromine is present in the molecular chain constituting the polymer fine particles, the polarity is increased. As a result, the polarity of the toner surface is also increased, and considering the low temperature fixability, even if the substance inside the toner exudes in a high temperature environment, there is little influence on the chargeability as a toner, and the four effects of the present invention can be achieved simultaneously. I think that it was possible to be satisfied.

  For the above reasons, the present inventors consider that the problems of the present invention have been solved.

  The appropriate range of the present invention will be described below.

  The primary particle number average particle diameter of the silica of the present invention is preferably 80 to 300 nm. More preferably, it is 90 to 280 nm.

  When the number average particle diameter is less than 80 nm, it becomes difficult to exhibit high transfer efficiency in the toner having circularity according to the present invention. When the number average particle diameter exceeds 300 nm, it becomes difficult to make strong adhesion to the toner surface, and there are many desorbing substances, resulting in unsatisfactory resistance to member contamination.

  The primary particle number average particle diameter of the titanium oxide of the present invention is preferably 10 to 100 nm. More preferably, it is 15 to 90 nm. When the number average particle diameter is less than 10 nm, embedding in the toner surface occurs during continuous printing, and the charging property of the toner surface becomes insufficient, and good transfer uniformity cannot be obtained. When the number average particle diameter exceeds 100 nm, it is difficult to firmly adhere to the toner surface, there are many that are detached, and the stain resistance of the member is not satisfied.

  The peak molecular weight of the THF soluble component of the present invention is preferably 10,000 to 35,000. More preferably, it is 15000 to 30000. When the peak molecular weight is less than 10000, toner adhesion to a functional member involved in the development process, for example, the surface of the toner carrier, in continuous printing is induced, resulting in image defects. When the peak molecular weight exceeds 35,000, the low-temperature fixing effect of the present invention cannot be fully exhibited.

The specific surface area of the toner of the present invention is preferably 2.00 to 7.00 m ² / g. More preferably, it is desired to be 2.50 to 5.00. When the specific surface area is less than 2.00 m ² / g, for example, when the circularity of the toner is large, embedding of inorganic fine powder on the toner surface is facilitated in continuous printing, and desired transfer uniformity is maintained. It becomes difficult to do. When the specific surface area exceeds 7.00 m ² / g, it becomes difficult to exhibit high transfer efficiency in the toner having the circularity of the present invention. Further, it is difficult to maintain desired transfer uniformity even in continuous printing.

  The toner of the present invention preferably has a Si / Ti intensity ratio of 4.5 to 22.0. More preferably, it is desired to be 5.0 to 18.0. When the Si / Ti strength ratio is less than 4.5, the effect of adding silica cannot be exhibited, the effect on the high transfer efficiency is diminished, and further, the contamination resistance of the member does not satisfy the effect of the present invention. When the Si / Ti strength ratio exceeds 22.0, the effect of adding titanium oxide cannot be exhibited, and the effect related to transfer in continuous printing is not what the present invention desires.

  The average circularity of the toner of the present invention is preferably 0.950 to 0.980. More preferably, it is desired to be 0.960 to 0.975. When the average circularity is less than 0.950, it is difficult to exhibit high transfer efficiency. When the average circularity exceeds 0.980, embedding of the inorganic fine powder on the toner surface is easily promoted in continuous printing, and it becomes difficult to maintain desired transfer uniformity.

  The total amount of the inorganic fine powder of the toner of the present invention is preferably 2.0 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. More preferred is 2.5 to 4.5 parts by mass. When the total amount of the inorganic fine powder is less than 2.0 parts by mass, it is difficult to obtain the transfer uniformity required by the present invention due to the small amount of the inorganic fine powder embedded on the toner surface in continuous printing. When the total amount of the inorganic fine powder exceeds 5.0 parts by mass, it becomes difficult to firmly adhere the inorganic fine powder to the toner surface, and since there are many detachables, is the contamination resistance to the member satisfactory? Disappear. Further, if the heat transfer property to the toner is deteriorated, the low-temperature fixability is deteriorated.

  The bromine content of the toner of the present invention is preferably 200 to 1200 ppm. More preferably, it is desired to be 250 to 800 ppm. If the bromine content of the toner is less than 200 ppm, it is suggested that the effect as a chain transfer agent is insufficient, and the low-temperature fixability is not satisfactory. When the bromine content of the toner exceeds 1200 ppm, toner odor becomes a problem.

  The ratio D4 / D1 of the weight average particle diameter D4 and the number average particle diameter D1 in the Coulter counter of the toner of the present invention is preferably 1.000 to 1.350. More preferably, it is 1.000 to 1.280. When D4 / D1 of the toner exceeds 1.350, it means that the toner particle size distribution is wide, and it becomes difficult to uniformly deposit the inorganic fine powder on the toner surface, and the high transfer efficiency which is an effect of the present invention is achieved. And transfer uniformity is poor.

  The MD1 hardness of the toner carrier used in the present invention is preferably 20.0 to 40.0. More preferably, it is 22.0 to 40.0. When the MD1 hardness of the toner carrier is less than 20.0, since the surface is soft, the toner is likely to be filmed in continuous printing, resulting in image defects.

  When the MD1 hardness of the toner carrier exceeds 40.0, in continuous printing, deterioration of transfer uniformity and deterioration of member resistance due to inducing toner deterioration of the present invention occur.

  The surface roughness Ra of the toner carrier used in the present invention is preferably 0.5 to 2.5 μm. When the surface roughness Ra is less than 0.5 μm, the toner layer on the toner carrier is thinned and the development efficiency is lowered. As a result, the high transferability and transfer uniformity have the effects of the present invention. I'm not satisfied. If the surface roughness Ra exceeds 2.5 μm, it is difficult to make the toner layer thin on the toner carrier, which causes a negative effect on uniform charging of the toner. The effect of the present invention is not satisfied.

  For the polymer fine particles used in the present invention, the following polymerizable monomers are used.

  Specifically, as the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrene derivative such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl accelerator Acrylic polymerizable monomers such as N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl meta Methacrylic polymerizable monomers such as relate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  The above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  In the present invention, it is particularly preferable to use a vinyl-based polymerizable monomer in order to further exhibit the effect.

  As the polymer fine particle cross-linking agent used in the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  In order to provide an insoluble difference, a crosslinking reaction is carried out with a crosslinking agent when the polymer fine particles are produced. The amount of the crosslinking agent may be 0.01 to 5.00 parts by mass, more preferably 0.03 to 3.00 parts by mass per 100 parts by mass of the binder resin.

  Examples of the chain transfer agent used in the present invention include n-pentyl mercaptan, isopentyl mercaptan, 2-methylbutyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-nonyl mercaptan. Alkyl mercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, n-pentadecyl mercaptan, n-hexadecyl mercaptan, t-hexadecyl mercaptan, stearyl mercaptan, thiol Alkyl esters of glycolic acid, alkyl esters of mercaptopropionic acid, carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl benzene bromide, Bromide ethane, halogenated hydrocarbons such as such as a halogenated hydrocarbon compound ethane dichloride include α- methylstyrene dimer. These chain transfer agents may be used alone or in combination of two or more. More preferably, halogenated hydrocarbons are desired.

  A preferable addition amount of the chain transfer agent is 0.05 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  As the polymerization initiator used in the polymerization of the polymerizable monomer used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used.

  For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide Oxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumylper Kisaido, t- butyl hydroperoxide, di -t- butyl peroxide, include peroxide initiators such as cumene hydroperoxide.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  Examples of the cationic surfactant used as an emulsifier used in the present invention include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.

  Nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, monodecanoyl sucrose, etc. Can be mentioned.

  An example of the material used for the colorant particle of the present invention is given, but other materials may be used.

  As the black colorant, carbon black, which is toned to black using the yellow / magenta / cyan colorant shown below, is used.

  As the colorant used in the present invention, known pigments can be used, and those shown below are representative.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3.7.10.12.12.14.15.17.23.3.24.6.2.62.73.74.74.75.83.93.95.99.9.100.101.104.108.109 110.111.117.123.128.129.138.139.147.148.1500.1166.168.169.177.179.180.181.183.185.191: 1.1191.192.193 .199 or the like is preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48; 2, 48; 3, 48; 4, 57; 1, 81; 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

  The external additives used in the present invention include inorganic fine powders such as silica, silicone resin, titanium oxide (anatase type, rutin type, non-crystalline), aluminum oxide, strontium titanate, cerium oxide, magnesium oxide, silicon nitride. Nitrides such as silicon carbide, carbides such as silicon carbide, metal salts such as calcium sulfate, barium sulfate, and calcium carbonate, carbon fluoride, hydrotalcite, and the like. Examples of the organic fine powder include PMMA resin and charge control agent.

  As a method for producing silica used in the present invention, an arbitrary method such as a dry method or a wet method is used. The dry method is a method for producing silicon tetrachloride by burning it at a high temperature together with a mixed gas of oxygen, hydrogen, and a diluent gas (for example, nitrogen, argon, carbon dioxide, etc.). In order to produce silica with a large particle size, a sol-gel method in which alkoxysilane is hydrolyzed and condensed with a catalyst in an organic solvent containing water, and then the solvent is removed from the resulting silica sol suspension and dried. Is preferably used. Alternatively, fine powder having a structure in which inorganic fine particles other than silica are used as a core and the surface is coated with silica may be used.

  Specific examples of the alkoxysilane used in the sol-gel method include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. In addition, as a catalyst for promoting hydrolysis and condensation reaction of alkoxysilane, basic catalysts such as ammonia, urea, monoamine, quaternary ammonium salt and the like are used. As the organic solvent used in the hydrolysis and condensation reaction step, alcohols are preferable. In this hydrolysis and condensation reaction, an alkoxysilane is added to water and an organic solvent in which a catalyst is present, and is preferably stirred at a temperature of 0 to 100 ° C. to prepare a silica sol suspension. At this time, the amount of water and catalyst, the type and concentration of alkoxysilane affect the particle size, particle size distribution, specific gravity and the like of the particles to be produced, so optimization is performed so that these are within a preferable range.

  For hydrophobizing silica (oil treatment), silicone oil is essential as a hydrophobizing agent, but a silane coupling agent may be used in combination. Examples of the silicone oil include those represented by the following formula.

（式中、ＲはＣ１乃至３のアルキル基を示し、Ｒ’はアルキル、ハロゲン変性アルキル、フェニル、変性フェニルの如きシリコーンオイル変性基を示し、Ｒ”はＣ１乃至３のアルキル基又はアルコオキシ基を示す。ｎ，ｍは整数を示す。）

(Wherein R represents a C1 to C3 alkyl group, R ′ represents a silicone oil-modified group such as alkyl, halogen-modified alkyl, phenyl or modified phenyl, and R ″ represents a C1 to C3 alkyl group or an alkoxy group. N and m are integers.)

  Examples of such silicone oil include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil preferably has a viscosity at 25 ° C. of 50 to 1000 centistokes. More preferably, it is 50 to 500 centistokes.

  As silane coupling agents, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexa Examples include methyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane.

  Further, a nitrogen-containing silane coupling agent may be used in order to impart positive frictional charging characteristics. Nitrogen-containing silane coupling agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, mono Butylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ- And propylbenzylamine.

  The hydrophobized degree of the surface-treated inorganic fine powder can be used as 60 to 99%, but preferably 80 to 99%.

  Examples of the method for producing titanium oxide used in the present invention include vapor phase oxidation of titanium halogen compounds and titanium alkoxides.

  Titanium oxide can be used in any of anatase type, rutin type, and amorphous, and may or may not be hydrophobized. More preferably, the hydrophobizing treatment is good, and when the hydrophobizing treatment is performed, either a wet method or a dry method may be used.

  Examples of hydrophobizing agents include silane coupling agents, titanium coupling agents, aluminate coupling agents, zircoaluminum coupling agents, and silicone oils. Of these, a silane coupling agent is particularly preferably used.

General formula Rm SiYn
[In the formula, R represents an alkoxy group, Y represents a hydrocarbon group such as an alkyl group, a vinyl group, a glycidoxy group, or a methacryl group, m represents an integer of 1 to 3, and n represents an integer of 1 to 3. Show. ]
The thing represented by is mentioned.

  Of the silane coupling agents, a monoalkyltoalkoxysilane coupling agent is particularly preferable. Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltri Methoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, n-butylto Silane, include n- octyl trimethoxysilane. The surface-treated inorganic fine powder can be used with a degree of hydrophobicity of 30 to 95%, preferably 45 to 80%.

  The toner of the present invention may be used in combination with wax.

  Examples of the wax used in the toner of the present invention include candelilla wax, carnauba wax, rice wax, tree wax, plant wax such as jojoba oil, animal wax such as beeswax, lanolin and spermaceti, montan wax, ozokerite and Mineral waxes such as ceresin, paraffin wax, microcrystalline wax, petroleum waxes such as petrolatum, synthetic hydrocarbons such as polyolefin wax and Fischer tropish wax, amide wax, ketone wax, ester wax, higher fatty acid, higher fatty acid metal salt Long chain alkyl alcohols. If necessary, these may be grafted, blocked or distilled.

  In order to express the above effects, carnauba wax, rice wax, montan wax, paraffin wax, microcrystalline wax, polyolefin wax, Fischer tropish wax, ester wax, amide wax, and ketone wax are preferable, and carna wax is more preferable. Uba wax, rice wax, paraffin wax, polyolefin wax, Fischer tropish wax, ester wax, amide wax, and ketone wax are desired.

  The wax fine particles used in the present invention are obtained by emulsifying the wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants, and nonionic surfactants.

  The added amount of the wax is 1.00 to 40.00 parts by mass, more preferably 3.00 to 30.00 parts by mass with respect to 100 parts by mass of the toner particles. Among these waxes, those having an endothermic peak in a differential thermal analysis of 40 ° C. to 110 ° C. are preferable, and those having a temperature of 45 ° C. to 90 ° C. are more preferable.

  The toner of the present invention may be used in combination with a charge control agent. The following substances are used for controlling the toner to be negatively charged. Although an example is given, things other than these may be used.

  For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and the like can be mentioned.
The following substances are used to control the toner to be positively charged. An example is given, but other examples may be used.

  Modified products of nigrosine, such as nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; analogs thereof Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; Over DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate, and the like. These can be used alone or in combination of two or more.

  The charge control agent may be used in an amount of 0.01 to 10.00 parts by mass, more preferably 0.50 to 5.00 parts by mass, per 100 parts by mass of the binder resin. The charge control agent is also used as an emulsion (charge control agent fine particles) having an average particle diameter of 0.01 to 3.00 μm in water.

  The molecular weight of the THF soluble content of the polymer particles used in the present invention is measured, for example, by the following measuring method.

A solution obtained by allowing the toner to stand in THF at room temperature for 24 hours and dissolving it is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, and measurement is performed under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of the component soluble in THF may be 0.5 mass%.
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, a calibration curve was obtained from standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F- manufactured by Tosoh Corporation). 20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

  The specific surface area of the toner used in the present invention is measured, for example, by the following measuring method.

  The measurement method of the BET specific surface area used in the present invention is measured by using a degassing device Bacuprep 061 (manufactured by Micromestic) and a BET measuring device Gemini 2375 (manufactured by Micromesotic). It is a sample preparation procedure. First, after measuring the mass of an empty sample cell, the sample to be measured is filled so as to enter between 2 g, the sample cell filled with the sample is set in the degassing device, and the room temperature is set. Degas for at least 3 hours. After completion of degassing, the mass of the entire sample cell is measured, and the accurate mass of the sample is calculated from the difference from the empty sample cell. A procedure for measuring the BET specific surface area will be described. First, empty sample cells are set in the balance port and analysis port of the BET measuring device. Next, a Dewar bottle containing liquid nitrogen is set at a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the prepared sample cell is set in the analysis port, the sample mass and P0 are input, and the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

  The average circularity of the toner used in the present invention is measured by the following method.

  The circularity of the toner in the present invention is used as a simple method for quantitatively expressing the shape of the toner, and was calculated using the following formula.

  Here, the “particle projected area” is the area of the binarized toner image, and the “peripheral length of the particle projected image” is defined as the length of the contour line obtained by connecting the edge points of the toner image. .

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner. When the toner is a perfect sphere, the circularity is 1.000. The more complicated the surface shape, the smaller the circularity. The average circularity C, which means the average value of the frequency distribution of circularity, is calculated from the following equation, where the circularity (center value) at the division point i of the particle size distribution is ci and the frequency is fci.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a dispersing means, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) having a φ5 mm titanium alloy chip as a vibrator is used and subjected to a dispersion treatment for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not become 40 degree | times or more.

  The measurement of the present invention uses a flow type particle image measuring apparatus “FPIA-1000 type” (manufactured by Toa Medical Electronics Co., Ltd.). The concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 / μl, 1000 or more toners are measured, and the number based on the equivalent circle diameter distribution and the prescribed equivalent circle diameter are obtained. The proportion of particles (number%) is measured. The results (frequency% and cumulative%) can be obtained by dividing the particle size range of 0.06 to 400 μm as shown in Table 1 into 226 channels (divided into 30 channels per octave). After the measurement, the average circularity of the toner and the particle size of 0.6 to 2.0 μm are obtained using this data.

  The particle size of the toner used in the present invention in a Coulter counter is measured by the following method.

  Measurement of toner particle size distribution: As a measuring device, for example, Coulter Counter TA-II, Coulter Multisizer II (manufactured by Coulter) or Coulter Multisizer III (manufactured by Coulter) is used. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the above electrolytic aqueous solution, and 5 mg of a measurement sample (toner) is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser, and the volume and number of toner particles are measured for each channel by using the 100 μm aperture as the aperture by the above-described measuring apparatus. Volume distribution and number distribution are calculated. A weight-average toner weight average particle diameter D4 (μm) obtained from the volume distribution of toner particles is obtained (the median value of each channel is a representative value for each channel).

  Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32 to 40.30 μm are used.

  The bromine content of the toner used in the present invention can be measured by the following method.

  For measurement of fluorescent X-rays, RIX3000 manufactured by Rigaku Denki Kogyo Co., Ltd. is used. For measuring the Kα-ray intensity of Br, LiF1 was used as the spectroscopic crystal at 50 mA · 50 kV, and SC (scintillation counter) was used as the detector. In the quantification method, all metal sensitivity curves are set in advance, and FP (fundamental parameter) quantification is performed using a compound composed of carbon and hydrogen as a balance component. An ion chromatography method may be used.

  The Si / Ti intensity ratio used in the present invention can be measured by the following method.

  For measurement of fluorescent X-rays, RIX3000 manufactured by Rigaku Corporation is used. For measuring the Kα line intensity of Si, PET was used as a spectroscopic crystal at 50 mA · 50 kV, and PC (proportional counter) was used as a detector. For the measurement of Ti Kα radiation intensity, LiF1 was used as a spectroscopic crystal at 50 mA · 50 kV, and SC (scintillation counter) was used as a detector.

  The intensity ratio of fluorescent X-rays in the present invention refers to the net intensity (KCPS) of Kα rays of Si and Ti elements, and the X-ray net intensity (KCPS) of Si / X-ray net intensity (KCPS) of Ti. The respective ratios were calculated to obtain the ratio.

  The degree of hydrophobicity of the inorganic fine powder used in the present invention can be measured by the following method.

  The methanol titration test is performed as follows. The methanol titration test is a test for confirming the degree of hydrophobicity of an inorganic fine powder having a hydrophobized surface. 0.2 g of hydrophobized inorganic fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the burette until the entire titanium oxide fine powder is wet. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed when the total amount of fine titanium oxide powder is suspended in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

  The maximum endothermic peak temperature of the wax used in the present invention can be measured by the following method.

  Performed according to “ASTM D 3418-82”. For the measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and measurement is performed at a heating rate of 10 ° C./min.

  The MDI hardness of the toner carrier used in the present invention can be measured by the following method.

  The MD-1 hardness of the roller provided with the surface layer is 5 hours or more in an environment of normal temperature and normal humidity (23 ° C., 55% RH) using a micro rubber hardness meter MD-1 type, Type A (manufactured by Kobunshi Keiki Co., Ltd.). For the roller that was left unattended, the vicinity of the central portion of the roller was measured over five points, and the average value was obtained.

  The surface roughness Ra of the toner carrier used in the present invention can be measured by the following method.

  Based on JIS surface roughness “JIS B 0601 (2001)”, this corresponds to the centerline average roughness measured using a surface roughness measuring instrument (“Surfcoder SE-30H” manufactured by Kosaka Laboratory Ltd.). Specifically, a 2.5 mm portion as the measurement length a is extracted from the roughness curve in the direction of the center line, the center line of this extraction portion is the X axis, the direction of the vertical magnification is the Y axis, and the roughness curve is When expressed by y = f (x), it means a value obtained by the following formula expressed in micrometers (μm).

  The Asker-C hardness of the toner carrier used in the present invention was measured using an Asker-C spring rubber hardness meter (manufactured by Kobunshi Keiki Co., Ltd.) in accordance with the Japan Rubber Association Standard SRIS0101. The measured value is 30 seconds after the pressing needle is brought into contact with a roller left at room temperature and normal humidity (23 ° C., 55% RH) for 12 hours or more with a force of 10 N.

  The volume resistivity of the toner carrier used in the present invention can be measured by the following method.

  The measurement sample is pressed against a metal drum and adjusted so that the roller penetration amount is 50 μm. Next, the rotation speed of the roller was rotated at 60 rpm, a voltage of 100 V was applied to the shaft body of the metal drum and the conductive roller, and the resistance value was calculated by measuring the current value flowing through the conductive roller.

  The electrostatic charge developing toner of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, the carrier may be a magnetic material such as iron powder, magnetite powder, ferrite powder, or a known material such as a mono or magnetic carrier with a resin coating on the surface thereof. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

  In the toner manufacturing method of the present invention, an aggregation method including an aggregation step and an aging step is used. Although a detailed method is shown below, it is not limited.

  The polymer fine particles can be produced by any method.

  Examples of the method for producing vinyl polymer fine particles include an emulsion polymerization method and a soap-free emulsion polymerization method. Examples of the method for producing polyester fine particles include a method in which the polyester is dissolved and neutralized in a suitable solvent and then phase-inverted and emulsified, or the polyester is dissolved in a suitable solvent and dispersed in an aqueous phase using a disperser. There are methods to make An arbitrary surfactant may be used in combination at the time of dispersion.

  The polyester is obtained, for example, by polycondensing an alcohol component and a carboxylic acid component in the presence of an ester catalyst, preferably at 150 to 280 ° C.

  In the aggregating step, for example, a pH adjuster, an aggregating agent, and a stabilizer are added and mixed in at least a mixed liquid of polymer particle dispersion and colorant fine particle dispersion, and temperature, mechanical power, etc. are appropriately added. To form in the liquid mixture. If necessary, the wax fine particles and the charge control agent fine particles may be co-aggregated simultaneously or in separate steps. Further, the colorant, wax, and charge control agent may be subjected to seed polymerization in advance.

  Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. It is done.

  Examples of the stabilizer mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in the aqueous dispersion is anionic, a cationic one can be selected as the stabilizer. The addition / mixing of the flocculant and the like is preferably performed at a temperature below the glass transition point of the resin contained in the mixed solution. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using, for example, a known mixing device, a homogenizer, a mixer and the like. The average particle size of the aggregated particles formed here is not particularly limited, but is usually controlled to be about the same as the average particle size of the toner to be obtained. The control can be easily performed, for example, by appropriately setting and changing the temperature and the stirring and mixing conditions.

  In the aging step of the present invention, before entering the fusing step, the pH adjusting agent, the polar surfactant, the nonpolar surfactant, etc. can be appropriately added in order to prevent fusing between the toner particles. . The heating temperature may be at least the glass transition temperature of the resin contained in the aggregated particles. In addition, the said heating can be performed using a publicly known heating apparatus and instrument. As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low.

  The toner carrier used in the present invention is produced by the following method.

  The toner carrier used in the image forming apparatus of the present invention can be configured to have a conductive elastic layer 2 on the outer periphery of a highly conductive shaft 1 as shown in FIG. At this time, the conductive elastic layer 2 may be a single layer or a multilayer.

  In addition, the toner carrier used in the image forming apparatus of the present invention may have a configuration in which a conductive resin layer 3 is further provided on the conductive elastic layer 2 as shown in FIG. .

  The toner carrier having this configuration is most preferable for exhibiting the effects of the present invention. Each of the conductive elastic layer 2 and the conductive resin layer 3 may be a single layer or multiple layers.

  As the above-mentioned highly conductive shaft 1, any one can be used as long as it has good conductivity. Usually, the outer diameter is 4.0 to 10.0 mm made of aluminum, iron, SUS, or the like. A metal cylinder is used.

The conductive elastic layer 2 formed on the outer periphery of the highly conductive shaft 1 uses an elastomer such as EPDM (ethylene-propylene-diene copolymer rubber) or urethane, or other resin molding as a base material. In addition, an electronic conductive material such as carbon black, metal, metal oxide, or an ionic conductive material such as sodium perchlorate is blended, so that an appropriate resistance region (volume resistivity) is 10 ^{3 to} 10 ⁸ Ωcm. Form with adjusted materials. The hardness of the conductive elastic layer is preferably 15 to 40 degrees in terms of ASKER-C hardness. The thickness of the conductive elastic layer can be 1.0 to 6.0 mm.

  Specific examples of the base material include polyurethane, natural rubber, butyl rubber, nitrile rubber, polyisoprene rubber, polybutadiene rubber, silicone rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, chloroprene rubber, Acrylic rubber and mixtures thereof are mentioned. Silicone rubber or EPDM (ethylene-propylene-diene rubber) is preferably used.

  Examples of the electronic conductive material used for imparting conductivity to the conductive elastic layer 2 include conductive carbon such as ketjen black EC and acetylene black, SAF, ISAF, HAF, FEF, GPF, SRF, FT, Examples thereof include carbon for rubber such as MT, carbon for color (ink) subjected to oxidation treatment, and metals and metal oxides such as copper, silver, and germanium. Among these, carbon black (conductive carbon, carbon for rubber, carbon for color (ink), etc.) is preferable because the conductivity can be easily controlled with a small amount. These conductive powders are usually suitably used in a range of 0.5 to 50.0 parts by mass, particularly 1.0 to 30.0 parts by mass with respect to 100 parts by mass of the base material.

  Examples of the ion conductive material used to impart conductivity to the conductive elastic layer 2 include inorganic ion conductive materials such as sodium perchlorate, lithium perchlorate, calcium perchlorate, and lithium chloride. Examples thereof include organic ionic conductive substances such as modified aliphatic dimethyl ammonium etosulphate and stearyl ammonium acetate.

  The conductivity imparting agent such as the electron conductive material or the ion conductive material is used in an amount necessary for making the conductive elastic layer have an appropriate volume resistivity as described above. Usually, it is suitably used in the range of 0.5 to 50.0 parts by mass, particularly 1.0 to 30.0 parts by mass with respect to 100 parts by mass of the substrate.

  As the base material of the conductive resin layer 3 that covers the conductive elastic layer 2 of the conductive roller having the configuration shown in FIG. 2, polyamide resin, urethane resin, urea resin, imide resin, melanin resin, fluorine resin, phenol Examples thereof include resins, alkyd resins, silicone resins, polyester resins, polyether resins, and the like, and mixtures thereof. Urethane resin is preferably used as a base material for the conductive resin layer 3 because it has a large ability to charge toner by friction and has wear resistance.

At this time, the urethane resin is composed of an isocyanate component and a polyol component. As this polyol component, polyether polyol, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polyolefin polyol, polymer polyol and the like are used, but as a polyol that effectively promotes the present invention, polyether polyol is good,
Specifically, a unit (BO) represented by the following formula (1)

（式中ｌは正の整数を示す。）

(In the formula, l represents a positive integer.)

  Unit (PO) represented by the following formula (2)

（式中ｍは正の整数を示す。）
で示されるユニットが用いられるポリエーテルポリオールに含まれることが好ましい。

(In the formula, m represents a positive integer.)
It is preferable that it is contained in the polyether polyol used.

  At this time, polyether polyol in which all the units represented by formula (1) and formula (2) are contained in one molecule, or at least one unit represented by formula (1) and formula (2) is contained in one molecule. Any of the polyether polyols contained above can be used. The polyether polyol used as a raw material for urethane is preferably adjusted so as to include all the units represented by the formulas (1) and (2).

  At this time, the polyether polyol (BO) having a unit represented by the formula (1) has a type having two or more hydroxyl groups, and the polyether polyol (PO) having a unit represented by the formula (2) has a hydroxyl group. It is preferable to use one of each having one because the effect of the present invention is promoted.

  Specific examples of the isocyanate component of the urethane resin include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), Examples thereof include phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI), and cyclohexane diisocyanate. Among these, aromatic isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), phenylene diisocyanate (PPDI), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI) preferable. In particular, diphenylmethane diisocyanate (MDI) is preferable because it can improve the restorability of the toner carrier after local loading.

  This isocyanate component is adjusted so that the mass ratio with respect to the total polyol used is isocyanate: polyol = 20: 80 to 60:40.

The conductive resin layer 3 is adjusted to 10 ^{4 to} 10 ¹⁰ Ωcm as an appropriate resistance region (volume resistivity) by blending the base material with a conductivity-imparting agent such as an electronic conductive material or an ionic conductive material. The material is made of. The conductive resin layer preferably has a thickness in the range of 5.0 to 40.0 μm, and the surface roughness Ra is preferably 0.5 to 2.5 μm. The MD1 hardness is preferably 20 to 40.

  The thickness of the conductive elastic layer or conductive resin layer of the present invention was determined by cutting a roller on which the conductive elastic layer and the conductive surface layer were formed, measuring the cross-section at nine points, and calculating the average value. When the thickness was thin as in the case of a conductive resin layer, the cross section was measured at 9 points with a video microscope (magnification 2000 times) and the average value was obtained.

  The kneading of the resin serving as the base material and the conductivity-imparting agent such as an electronic conductive material or an ionic conductive material is performed using a ball mill or the like to form a rough surface for forming the toner carrier surface roughness as needed. After the particles are added and dispersed, the curing can be carried out by adding a curing agent or a curing catalyst or the like at an appropriate time and stirring. The obtained composition is applied by a method such as spraying or dipping. Alternatively, a conductive elastic layer or a conductive resin layer is integrally formed by injecting the obtained composition into a cavity of a molding die in which a core metal is pre-arranged, and heating to cause reaction hardening or solidification. A method of cutting into a predetermined shape and dimensions such as a tube shape by cutting or the like from a slab or block separately formed using the above composition in advance, and press-fitting a core metal into this to conduct electricity on the core metal Examples thereof include a method of manufacturing by coating an elastic layer or a conductive resin layer, a method of appropriately combining these methods, and the like. If desired, the outer diameter may be further adjusted to a predetermined outer diameter by cutting or polishing treatment.

  Examples of the roughened particles include rubber particles such as EPDM (ethylene-propylene-diene copolymer rubber), NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), CR (chloroprene rubber), and silicone rubber. Or elastomer particles such as polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide-based thermoplastic elastomer (TPE), or PMMA particles, urethane resin particles, fluorine resin, silicone resin, phenol resin, naphthalene resin, furan resin Resin particles such as xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, polyacrylonitrile resin can be used alone or in combination.

  Next, an example of a developing device and an image forming method for outputting an image of the toner produced in the present invention will be described. Note that the present invention is not limited to this.

  In FIG. 3, a developing device 10 is located in a developer container 12 containing a non-magnetic toner 11 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 12, and a latent image carrier (photosensitive). A drum) 13 and a toner carrier 14 disposed opposite to each other. The electrostatic latent image on the latent image carrier 13 is developed and visualized.

  The toner carrier 14 is horizontally provided with the substantially right half-peripheral surface shown in the drawing entering the developing container 12 at the opening, and the left substantially semi-peripheral surface exposed to the outside of the developer container 12. The surface exposed to the outside of the developing container 12 is in contact with the latent image carrier 13 located on the left side of the developing device 10 as shown in FIG.

  The toner carrier 14 is driven to rotate in the direction of arrow B, and the surface thereof has appropriate irregularities for increasing the probability of rubbing with the toner 11 and carrying the toner 11 well. As the toner carrier 14, an elastic roller can be used when the toner carrier 14 is used in contact with the latent image carrier 13 as shown in FIG. 3. The peripheral speed of the latent image carrier 13 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is rotated at a peripheral speed of 1 to 2 times the peripheral speed of the latent image carrier 13.

  At the upper position of the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane and silicone, or a metal thin plate of SUS or phosphor bronze having spring elasticity is used as a base, and the contact surface to the toner carrier 14. A regulating member 15 made of a rubber material bonded to the side is supported by the blade support metal plate 16 so as to abut the vicinity of the free end side on the outer peripheral surface of the toner carrier 14 by surface contact. Yes. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the toner regulating member, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the blade support metal plate 16 and the contact pressure against the toner carrier 14 is appropriately set. The linear pressure was converted from a value obtained by inserting three metal thin plates having a known friction coefficient into the abutting portion and pulling out the central one with only a spring.

  The elastic roller 17 is in contact with the contact portion of the toner regulating member 15 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. Examples of this structure include a foamed skeleton-like sponge structure and a fur brush structure in which fibers such as rayon and nylon are planted on a cored bar in terms of supplying the toner 11 to the toner carrier 14 and stripping off the undeveloped toner. To preferred. As an example of the elastic roller, an elastic roller 17 having a diameter of 12 mm in which a polyurethane foam is provided on the core metal 17a is used. The contact width of the elastic roller 17 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  The toner charging roller 18 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 19. The contact load of the toner charging roller 18 on the toner carrier 14 by the suppressing member 19 was set to 0.49 to 4.9N. Due to the contact of the toner charging roller 18, the toner layer on the toner carrier 14 is closely packed and uniformly coated. The longitudinal positional relationship between the elastic blade 15 and the toner charging roller 18 is preferably arranged so that the toner charging roller 18 can reliably cover the entire contact area of the elastic blade 15 on the toner carrier 14.

  In addition, for driving the toner charging roller 18, it is essential to follow or have the same peripheral speed with the toner carrier 14, and when the peripheral speed difference occurs between the toner charging roller 18 and the toner carrier 14, the toner coat is not uniform. And unevenness occurs on the image, which is not preferable.

  The bias of the toner charging roller 18 is applied with a direct current (20 in FIG. 3) applied between the toner carrier 14 and the latent image carrier 10 by the power source 20, and the toner 11 on the toner carrier 14 is Charge is applied from the toner charging roller 18 by discharging.

  The bias of the toner charging roller 18 is equal to or higher than the discharge start voltage having the same polarity as that of the toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the toner carrier 14.

  After being charged by the toner charging roller 18, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 13.

  In this developing section, the toner layer formed on the toner carrier 14 is formed by a DC bias applied between the toner carrier 14 and the latent image carrier 13 by the power source 20 as shown in FIG. The electrostatic latent image on the latent image carrier 13 is developed as a toner image.

  Although the above description has been given of the development method and the case where the present invention is applied to a process cartridge comprising a developing device detachable from the image forming apparatus main body, the developing apparatus is configured to be fixed in the image forming apparatus main body and replenish only toner. You may apply to. In addition, the photosensitive drum, cleaning blade, waste toner container, and charging device can be provided with at least the above-described developing device, or can be applied to a process cartridge that can be attached to and detached from the image forming apparatus main body. May be.

  The toner of the present invention can also be used in full color image formation. As an example of the full-color image forming method, the image forming method shown in FIG. 4 will be described. The configuration is not limited to that shown in FIG.

  Reference numeral 13 denotes a drum-shaped photoconductor as a first image carrier, which is rotationally driven at a predetermined peripheral speed (process speed) in the direction of the arrow in the figure. In the rotation process, the photosensitive member 13 is uniformly charged to a predetermined polarity and potential by the primary charger 18, and then subjected to exposure 30 by an image exposure unit (not shown). In this manner, an electrostatic latent image corresponding to the first color component image (for example, a yellow toner image) of the target color image is formed.

  Next, the electrostatic latent image is developed into a yellow toner image which is the first color by a first developing device (yellow toner developing device 41). At this time, the second to fourth developing units, that is, the magenta toner developing unit 42, the cyan toner developing unit 43, and the black toner developing unit 44 are not operated and do not act on the photosensitive member 13. One color yellow toner image is not affected by the second to fourth developing units.

  On the other hand, the intermediate transfer belt 31 is driven to rotate in the direction of the arrow at the same peripheral speed as the photosensitive member 13. The yellow toner image of the first color formed on the photoconductor 13 passes through the nip portion between the photoconductor 13 and the intermediate transfer belt 31 and is supplied from the bias power source 33 to the intermediate transfer belt 31 via the roller 32. The image is sequentially transferred onto the outer peripheral surface of the intermediate transfer belt 31 by the electric field formed by the applied bias. This process is called primary transfer, the roller 32 is called a primary transfer roller, and the applied bias is called a primary transfer bias. The surface of the photoconductor 13 after the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 31 is cleaned by the cleaning device 34.

  Similarly, the second color magenta toner image, the third color cyan toner image, and the fourth color black toner image are sequentially superimposed and transferred onto the intermediate transfer belt 31, and the full color toner corresponding to the target color image is obtained. An image is formed.

  Next, the color toner image is transferred to a transfer material, and this process is called secondary transfer. Reference numeral 35 denotes a secondary transfer roller, which is supported in parallel with the secondary transfer counter roller 36 and arranged in a state in which it can be separated from the lower surface of the intermediate transfer belt 31.

  A primary transfer bias for transferring the toner image from the photoreceptor 1 to the intermediate transfer belt 31 is applied from a bias power source 33 with a polarity opposite to that of the toner. The applied voltage is, for example, in the range of + 100V to + 2000V.

  In the primary transfer process of the first to third color toner images from the photoreceptor 1 to the intermediate transfer belt 31, the secondary transfer roller 35 can be separated from the intermediate transfer belt 31. For the full-color image transferred onto the intermediate transfer belt 31, the secondary transfer roller 35 is brought into contact with the intermediate transfer belt 31. On the other hand, the transfer material P is fed from the paper feed roller 37 to the contact portion between the intermediate transfer belt 31 and the secondary transfer roller 35 at a predetermined timing. Then, the secondary transfer bias is applied from the bias power source 38 to the secondary transfer roller 35, whereby the full color image on the intermediate transfer belt is secondarily transferred to the transfer material P. The transfer material P onto which the toner image has been transferred is introduced into the fixing device 39 and fixed by heating.

  After the image transfer to the transfer material P is completed, the toner (transfer residual toner) remaining on the intermediate transfer belt is scraped off by the cleaning blade 40 and carried to a waste toner box.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. A method for producing toner particles will be described below. Incidentally, all parts and percentages in the examples and comparative examples are based on mass unless otherwise specified.

(Method for producing polymer fine particle A)
A mixture of the following monomers / aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes. The reaction temperature is 70 ° C.

[Monomers]
Styrene 80.0 parts Butyl acrylate 20.0 parts Acrylic acid 3.0 parts Ethyl tribromide 0.5 parts Divinylbenzene 0.3 parts

[Initiator aqueous solution]
Potassium persulfate 10.0 parts Demineralized water 100.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare a polymer fine particle dispersion A.

(Method for producing polymer fine particle B)
The following monomers / initiator aqueous solution was reacted for 10 hours from the start of polymerization. Hold for another 30 minutes. The reaction temperature is 70 ° C.

[Monomers]
Styrene 80.0 parts Butyl acrylate 20.0 parts Acrylic acid 3.0 parts Ethyl tribromide 0.5 parts

[Initiator aqueous solution]
Potassium persulfate 10.0 parts Demineralized water 100.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare polymer fine particles B.

(Method for producing wax dispersion)
Heat 20.0 parts of pentaerythritol behenate (DSC peak temperature 80 ° C.), 2.5 parts of an anionic surfactant (Neogen SC Daiichi Kogyo Seiyaku Co., Ltd.) and 100.0 parts of demineralized water to 90 ° C. with a disper. Stir for 15 minutes. Subsequently, this dispersion was emulsified using a homogenizer (15-M-8PA type, manufactured by Gorin Co., Ltd.) under conditions of high-pressure shear of 95 ° C. and 50 kg / cm 2 to obtain a wax dispersion.

(Method for producing colorant fine particle dispersion)
To 100.0 parts of demineralized water, C.I. I. 20.0 parts of Pigment Red 122 and 7.0 parts of polyoxyethylene nonylphenyl ether were added and dispersed with a ball mill to obtain a magenta colorant fine particle dispersion.

  Similarly, C.I. I. Pigment Blue 15: 3, cyan colorant fine particle dispersion, C.I. I. Pigment YELLOW 180 was used to prepare a yellow colorant fine particle dispersion, and carbon black was used to prepare a black colorant fine particle dispersion.

(Method for producing charge control agent fine particle dispersion)
To 100.0 parts of demineralized water, 20.0 parts of a charge control agent 4,4′-methylenebis [2- [N- (4-chlorophenyl) amido] -3-hydroxynaphthalene], and alkylnaphthalene sulfonate 5.0 Was dispersed by a ball mill in the presence of a part to obtain a charge control agent fine particle dispersion.

(Toner production method)
<Magenta Toner No. 1>
-Polymer fine particle A dispersion 400.0 parts (as solid content)
-Colorant fine particle dispersion 40.0 parts (as solid content)
-Wax dispersion 1 80.0 parts (as solids)
The above was put into a reaction vessel for coagulation aging equipped with a stirrer, a cooling tube and a thermometer and stirred. This mixed solution was adjusted to pH = 5.0 using 1.0N aqueous potassium hydroxide solution.

  As a flocculant, 200.0 parts of a 20.0% aqueous sodium chloride solution is added dropwise to the above mixed solution over 30 minutes, and the reaction vessel is heated to 50 ° C. with stirring in an oil bath for heating. Retained. Further, the temperature was raised to 55 ° C. and held for 1 hour to prepare an aggregate (polymer fine particles + colorant fine particles + wax dispersion).

  After adding 5.0 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the reaction vessel was sealed and heated to 93 ° C. while continuing to stir using a magnetic seal for 5 hours. The agglomerates were held and aged, and then cooled to 30 ° C.

Furthermore, in the aggregate dispersion liquid,
-Charge control agent fine particle dispersion 2.0 parts (as solid content)
-Polymer fine particle B dispersion 100.0 parts (as solid content)
As a flocculant, 400.0 parts of a 20.0% sodium chloride aqueous solution was dropped, and the reaction vessel was heated to 50 ° C. with stirring in an oil bath for heating, and kept at 50 ° C. for 1 hour. Further, the temperature was raised to 55 ° C. and held for 1 hour to prepare an aggregate of (polymer fine particles + colorant fine particles + wax dispersion + charge control agent fine particle dispersion + polymer fine particle B dispersion).

  After adding 6.0 parts of an anionic surfactant (Daiichi Kogyo Seiyaku: Neogen SC), the reaction vessel was sealed and heated to 93 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained and aged.

  The slurry is cooled with stirring and washed with water. The washing method was carried out using 12 times the amount of water of the slurry (6 times the amount of water × 2 times) and dried at 40 ° C. to obtain magenta particles.

Next, the following inorganic fine powder: silica hydrophobized with dimethyl silicone oil (hydrophobicity: 95%) 2.5 parts: titanium oxide hydrophobized with isobutyltrimethoxysilane (hydrophobicity: 52%) After adding 2 parts in a ball mill and mixing for 30 seconds, 100 parts of the obtained toner particles were added with the mixed inorganic fine powder, and a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) was used. Add magenta toner No. 3 for 3 minutes at 3000 rpm. 1 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 2>
In the production of the polymer fine particle B, magenta toner No. 1 was used except that 0.4 parts of ethyl tribromide acetate and 0.1 part of tetrachloromethane were used as chain transfer agents. 1 and magenta toner no. 2 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 3>
Except for changing the time of the aging process from 5 hours to 4 hours, the magenta toner no. 1 and magenta toner no. 3 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 4>
When the polymer fine particles A and B were produced, the magenta toner No. 1 was used except that the chain transfer agent ethyl tribromide acetate was changed from 0.5 parts to 0.8 parts. 1 and magenta toner no. 4 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 5>
Except for changing the average primary particle diameter of silica from 105 nm to 82 nm and changing the addition amount from 2.5 parts to 2.3 parts, the magenta toner No. 1 and magenta toner no. 5 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 6>
Except for changing the average primary particle diameter of the titanium oxide from 35 nm to 95 nm, the magenta toner no. 1 and magenta toner no. 6 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 7>
Except for changing the addition amount of silica from 2.5 parts to 2.4 parts and from 0.2 parts to 0.5 parts of titanium oxide, the magenta toner No. 1 and magenta toner no. 7 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 8>
A reactor equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen introducing tube was charged with 600 g of methyl ethyl ketone, and a polyester (polycondensate of propylene oxide-modified bisphenol A and phthalic acid: peak molecular weight = 5000, Tg = 70 g) was added and dissolved at room temperature. The resulting solution was neutralized by adding 6 g of triethylamine, followed by adding 2500 g of ion-exchanged water, and then distilling off methyl ethyl ketone at a temperature of 50 ° C. or lower under reduced pressure at a stirring speed of 300 revolutions / minute. A polyester fine particle dispersion is produced. The average particle diameter of the obtained particles was 0.3 μm.

  Except for changing the polymer fine particle B dispersion to the polyester fine particle dispersion and further changing the aging process time to 4 hours, the magenta toner no. 1 and magenta toner no. 8 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 9>
Magenta except that when the polymer fine particles A and B are produced, the chain transfer agent ethyl tribromide acetate is changed from 0.5 part to 0.3 part and the aging process time is changed to 3 hours. Toner No. 1 and magenta toner no. 9 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 10>
When producing the polymer fine particles A and B, the chain transfer agent ethyl tribromide acetate was changed from 0.5 part to 1.2 parts, respectively, and the polymerization temperature was changed from 70 ° C. to 73 ° C. , Magenta toner no. 1 and magenta toner no. 10 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 11>
When producing the polymer fine particles A and B, the chain transfer agent ethyl tribromide acetate was changed from 0.5 part to 0.1 part, respectively, and the polymerization temperature was changed from 70 ° C. to 65 ° C. , Magenta toner no. 1 and magenta toner no. 11 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 12>
The average primary particle diameter of silica is from 105 nm to 82 nm, the addition amount is from 2.5 parts to 3.0 parts, the average primary particle diameter of titanium oxide is from 35 nm to 95 nm, and the addition amount is from 0.2 parts to 0 parts. Except for changing to 1 copy, magenta toner no. 1 and magenta toner no. 12 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 13>
Except for changing the average primary particle diameter of silica from 105 nm to 82 nm, the average primary particle diameter of titanium oxide from 35 nm to 95 nm, and the addition amount from 0.2 parts to 1.2 parts, the magenta toner no. 1 and magenta toner no. 13 was obtained. The physical properties are shown in Table 2.

<Magenta Toner No. 14>
In producing the polymer fine particles A and B, the chain transfer agent ethyl tribromide acetate is changed from 0.5 part to 1.3 parts, respectively. The aging time after agglomeration of the polymer fine particles B is changed from 5 hours to 3 hours, and the anionic surfactant at this time is changed from 6.0 parts to 8.0 parts. Further, in the step of attaching the inorganic fine powder to the toner particles, the average primary particle diameter of silica is changed from 105 nm to 285 nm, the addition amount is increased from 2.5 parts to 3.0 parts, and the average primary particle diameter of titanium oxide is increased. Is changed from 35 nm to 95 nm, and the addition amount is changed from 0.2 part to 0.1 part. Other than this, magenta toner No. 1 and magenta toner no. 14 was obtained. The physical properties are shown in Table 2.

<Cyan Toner No. 1>
C. I. Pigment Red 122 as C.I. I. Except for changing to Pigment Blue 15: 3, magenta toner no. In the same manner as in No. 1, cyan toner no. 1 was obtained. The physical properties are shown in Table 2.

<Cyan Toner No. 2>
C. I. Pigment Red 122 as C.I. I. Except for changing to Pigment Blue 15: 3, magenta toner no. 14 and magenta toner no. 2 was obtained. The physical properties are shown in Table 2.

<Yellow Toner No. 1>
C. I. Pigment Red 122 as C.I. I. Except for changing to Pigment Yellow 180, magenta toner No. In the same manner as in yellow toner No. 1 1 was obtained. The physical properties are shown in Table 2.

<Yellow Toner No. 2>
C. I. Pigment Red 122 as C.I. I. Except for changing to Pigment Yellow 180, magenta toner No. In the same manner as in No. 14, yellow toner no. 2 was obtained. The physical properties are shown in Table 2.

<Black Toner No. 1>
C. I. Pigment Red 122 is changed to C carbon black. In the same manner as in No. 1, black toner no. 1 was obtained. The physical properties are shown in Table 2.

<Black Toner No. 2>
C. I. Except for changing Pigment Red 122 to carbon black, Magenta Toner No. In the same manner as in No. 14, black toner no. 2 was obtained. The physical properties are shown in Table 2.

(Method for producing toner carrier)
<Toner carrier No. 1>
A core metal (shaft body) with an outer diameter of 8 mm is placed concentrically in a cylindrical mold with an inner diameter of 16 mm, and a liquid conductive silicone rubber (manufactured by Toray Dow Corning Silicone Co., Ltd.) is used as a material for forming the conductive elastic layer. Was cast. Thereafter, it was placed in an oven at 130 ° C. and heat-molded for 30 minutes. After demolding, secondary vulcanization was carried out in an oven at 200 ° C. for 4 hours to form a conductive elastic layer having a thickness of 3 mm.

-2.2 functional polyether polyol having a unit represented by Formula 1 (TE5042, manufactured by Mitsui Takeda Chemical Company) 100.0 parts-Trifunctional polyether polyol having a unit represented by Formula 2 (G100 Mitsui Takeda Chemical Company) Manufactured) 10.0 parts ・ isocyanate (C2521 Nippon Polyurethane Industry Co., Ltd. solid content 65%) 125.0 parts Conductive resin prepared by adding methyl ethyl ketone to the above raw material mixture so as to have a solid content of 25 to 30% by mass A raw material solution for layer formation was obtained. To the solid content of this raw material liquid, 15 parts of carbon black MA230 (manufactured by Mitsubishi Chemical Corporation) and 15 parts of acrylic particles MX-1000 (manufactured by Soken Chemical Co., Ltd.) were added, and this paint liquid was stirred and dispersed with a ball mill. The obtained paint is applied on the conductive elastic layer previously molded by dipping so as to have a film thickness of 15 μm, dried in an oven at 80 ° C. for 15 minutes, and then cured in an oven at 140 ° C. for 5 hours to form a surface layer. Toner carrier No. having a conductive resin layer 1 was obtained. Table 3 shows the physical properties.

<Toner carrier No. 2>
Except for changing the carbon black from 15 parts to 10 parts and further changing the thickness of the conductive layer from 15 μm to 12 μm, the toner carrier No. In the same manner as in No. 1, the toner carrier No. 2 was obtained. Table 3 shows the physical properties.

<Toner carrier No. 3>
The toner carrier No. was changed except that the carbon black was changed from 15 parts to 25 parts and the conductive layer thickness was changed from 15 μm to 50 μm. In the same manner as in No. 1, the toner carrier No. 3 was obtained. Table 3 shows the physical properties.

  The evaluation method and evaluation criteria of the present invention will be described below.

(1) Low-temperature fixability In the image forming apparatus of the contact one-component developing system shown in FIG. 4, a developing device shown in FIG. Leave at (10 ° C./50% RH: A environment) for 48 hours. Thereafter, an unfixed image of an image pattern in which 9 points of 10 mm × 10 mm square images are evenly arranged on the entire transfer paper is output. A monochromatic toner loading amount outputs a halftone image of 0.3 mg / cm ² . The fixing start temperature was evaluated using the unfixed image. For the evaluation of the fixing area, Xerox 4024 (105 g / cm ² ) was used as the paper type. The fixing machine was an external fixing capable of controlling the temperature of a 40 mmφ heat roller without an oil application function, and measurement was performed under a fixing condition of 150 mm / sec. In addition, as the material of the roller at this time, a fluorine material was used for both the upper part and the lower part. The nip width was 6 mm. Further, the determination of the start of fixing is performed by rubbing a fixed image (including a low-temperature offset image) with a load of 50 g / cm ² on a sylbon [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)] The temperature at which the density reduction rate before and after rubbing was less than 20% was defined as the fixing start point.

(2) Transfer efficiency In the image forming apparatus of the contact one-component developing system shown in FIG. 4, the developing device shown in FIG. 3 is filled with 100 g of the toner described in the examples and comparative examples, and is in a high temperature and high humidity environment ( (30 ° C / 85% RH: B environment) for 48 hours. After that, the density detection correction is performed, and the main unit power is forcibly turned off while outputting all the solid images, and the weight per unit area of the toner before transfer on the photosensitive drum and the toner transferred to the intermediate transfer member is calculated. Measure the transfer efficiency as follows:
Transfer efficiency = toner transferred to intermediate transfer member / toner before transfer on photosensitive drum × 100
Evaluation was made into A, B, C, and D.
A: 92% or more B: 85% or more and less than 92% C: 75% or more and less than 85% D: Less than 75%

(3) Transfer Uniformity In the image forming apparatus of the contact one-component development system shown in FIG. 4, the developer shown in FIG. 3 is filled with 100 g of the toner described in the examples and comparative examples, and is in a high temperature and high humidity environment. Leave at (30 ° C./85% RH: B environment) for 48 hours. At this time, the transfer paper is also left as it is. Thereafter, density detection is corrected, and continuous output is performed using a chart with a printing ratio of 5%. The total number of output sheets is five, 100 sheets, 1000 sheets, when 2500 sheets, the toner bearing amount 0.30 mg / cm ² of a halftone whole image and the toner bearing amount 0.55 mg / cm ² of solid whole image, Xerox 4024 (75 g / cm ² ) and Xerox 4024 (105 g / cm ² ) were used for sampling to determine transfer uniformity. Evaluation was made into A, B, C, and D.
A: All types of transfer paper have excellent transferability, and there is no problem in practical use.
B: Although a slightly non-uniform transfer property is observed in a halftone image of 105 g / cm ² , other transfer papers have excellent transfer properties and are not problematic in practical use.
C: In the halftone image and solid image of 105 g / cm ² , non-uniform transferability is recognized, but 75 g / cm ² is excellent in transferability and may cause a problem in practical use. Low level.
D: All types of transfer paper have non-uniform transfer, and are likely to cause problems in actual use.

(4) Contamination resistance of member In the image forming apparatus of the contact one-component developing system shown in FIG. 4, the developing device shown in FIG. Leave in (22 ° C./15% RH: C environment) for 48 hours. Thereafter, density detection is corrected, and continuous output is performed using a chart with a printing ratio of 5%. The total number of output sheets is five, 100 sheets, 1000 sheets, when 2500 sheets, the toner bearing amount 0.30 mg / cm ² of a halftone whole image and the toner bearing amount 0.55 mg / cm ² of solid whole image, Xerox 4024 (75 g / cm ² ) was used for sampling and the resistance to contamination of members was determined. Evaluation was made into A, B, C, and D.
A: There is no member contamination on the toner charging roller and the toner carrying member, and the halftone and all solid images are at a level of no problem in actual use.
B: Although there is some contamination at both ends of the toner charging roller, there is no problem in practical use with no effect on halftone and all solid images. C: Contamination on the entire area of the toner charging roller and both ends of the toner carrier. Although there are four or less minor streaks at both ends of the solid whole area image, it is not a halftone whole area image and is unlikely to cause a practical problem.
D: Contamination is present in the entire area of the toner charging roller and the entire area of the toner carrier, and both the halftone image and the entire solid image are present on the entire surface of the streak-like image in the sheet-passing direction. level.

<Examples 1 to 14 and Comparative Examples 1 to 8>
The toner particles described in Table 2 and the toner carrier described in Table 3 were evaluated by the combinations described in Table 4. The results are listed in Table 5.

FIG. 3 is an axial sectional view showing an example of the developing roller of the present invention. FIG. 3 is an axial sectional view showing an example of the developing roller of the present invention. It is the schematic of the image development apparatus which performs nonmagnetic one-component contact development. It is the schematic of the image forming method which performs nonmagnetic one-component contact development.

Explanation of symbols

1 Highly conductive shaft (shaft)
2 conductive elastic layer 3 conductive resin layer 10 developing device 11 toner 12 developer container 13 latent image carrier (photosensitive drum)
14 Toner carrier 15 Elastic blade (regulating member)
16 Blade support sheet metal 17 Elastic roller 18 Toner charging roller 19 Suppressing member 20 Power source 21 Stirring means 22 Toner leakage preventing member 30 Exposure 31 Intermediate transfer belt 32 Primary transfer roller 33 Bias power supply 34 Cleaning device 35 Secondary transfer roller 36 Secondary transfer facing Roller 37 Paper feed roller 38 Power supply 39 Fixing device 40 Cleaning blade 41 Yellow toner developing device 42 Magenta toner developing device 43 Cyan toner developing device 44 Black toner developing device 45 Transfer material guide

Claims (4)

A aggregation toner having toner particles obtained through the step of causing aging processes and agglomerated body obtain at least polymer fine particles and colorant and fine particles are agglomerated aggregates,
The aggregated toner may have a titanium oxide primary particle here the number average particle diameter of 80 to 300nm silica primary particles here the number average particle size of 10 to 100 nm,
The toner has a THF-soluble peak molecular weight of 10,000 to 35,000, the toner has a specific surface area of 2.00 to 7.00 m ² / g, and the toner has a Si / Ti intensity ratio of 4.5 to An agglomerated toner characterized by being 22.0.   The aggregated toner according to claim 1, wherein the polymer fine particles are vinyl polymer fine particles produced by an emulsion polymerization method. Aggregation toner according to claim 1 or 2 average circularity of the aggregation toner is characterized by a 0.950 to 0.980. Aggregation toner according to any one of claims 1 to 3 bromine elementary charge of the agglomerated toner may be equal to 200 to 1200 ppm.

Images