KR100635286B1 - Non-magnetic monocomponent toner having excellent developing property at low temperature condition - Google Patents

Abstract

The present invention relates to a nonmagnetic one-component toner composition and a preparation method thereof. More specifically, the nonmagnetic one-component toner is coated with a spherical organic fine powder, hydrophobic silica, and fine metal oxide powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm on the surface of the toner base particles. The composition has a good flowability, so that the toner supply is smooth, PCR contamination and image quality deterioration are small, and the toner layer is uniformly formed on the developing roller, but no fusion occurs in the braid of the developing roller, and at the same time, it remains in a low temperature environment. Since the toner can improve the low temperature afterimage periodically appearing on the non-image portion, the toner can be usefully used for an image output apparatus adopting a nonmagnetic one-component developing method in which the developing roller and the photoreceptor contact each other.

Non-magnetic single component, toner, fluidity, spherical organic fine powder, fine metal oxide powder, hydrophobic silica

Description

Non-magnetic, one-component toner with excellent low-temperature development characteristics {NON-MAGNETIC MONOCOMPONENT TONER HAVING EXCELLENT DEVELOPING PROPERTY AT LOW TEMPERATURE CONDITION}

The present invention relates to a nonmagnetic one-component toner composition for use in an image output apparatus adopting a nonmagnetic one-component developing method in which a developing roller and a photoconductor are in contact with each other, and a manufacturing method thereof.

In general, the dry developing method of electrophotographic can be broadly divided into a two-component developing method using a two-component developer including a toner and a carrier and a one-component developing method using a one-component developer including only a toner without using a carrier. Among them, the one-component developing method can generally achieve miniaturization and low price of the developing device, and there is an advantage of easy maintenance. In addition, the one-component development method is further divided into a method using a magnetic toner and a method using a non-magnetic toner, and the method using a non-magnetic toner has the advantage that color printing is possible. Therefore, in recent years, copiers and printers using a nonmagnetic one-component development method have been widely used, and the printing speed has been remarkably improved.

A nonmagnetic one-component toner has a fluidity of the toner particle itself, unlike a toner of a two-component developing method using a two-component developer containing carrier particles for transporting toner particles or a magnetic toner using magnetic force to move the toner particles. This will greatly affect the movement of the toner. That is, in the non-magnetic one-component toner, fluidity is one of the most important physical properties among the toners, and the image quality, density, and fog of the copied or printed image are caused by toner transfer to the non-image part. Occurrence and the cleaning property of the toner are greatly influenced by the fluidity of the toner particles. In addition, insufficient fluidity of the toner particles may cause streaking contamination of the copied or printed image, which is applied to a developing roller and a sub-roller for supplying a nonmagnetic one-component toner to the developing roller. This is because the nonmagnetic one-component toner is stagnant in the region and the nonmagnetic one-component toner does not move smoothly to the developing roller surface.

In addition to the fluidity and toner fusion problems described above, one of the main considerations in the electrophotographic method is a toner characteristic problem related to charging of the photosensitive member. In general, the charging method of a copier or a printer is divided into a method of contacting a photosensitive member to be charged (for example, a corona charging method) and a method of contacting (for example, a roller charging method) with a low ozone generation. The roller charging method is widely adopted due to the advantages. However, the roller charging method charges the surface of the photosensitive member by contacting the photosensitive member with a primary charge roller (PCR). At this time, when toner adheres to the PCR surface and contamination occurs, fog and density spots appear on the developed image. This results in burn contamination. In particular, in a low temperature environment, the fluidity is lowered, so that the property of attaching to the PCR surface of the toner is strong, thereby lowering charging characteristics and inferring transfer efficiency.

In order to improve these problems, there is a method of including the peelable fine particles such as silica in the toner particles in order to improve the flowability and charging ability of the toner particles in a low temperature environment. This improves the transfer efficiency by lowering the adhesion between the toner and the drum by interposing the toner and the drum by using fine particles. In order to obtain high transfer efficiency, the coverage of the toner surface by the fine particles must be set high. There is a problem in that the amount of added is increased, deterioration of toner chargeability, adhesion of fine particles to the latent electrostatic image bearing member, filming, impairment of fixation, and the like occur. In particular, since silica particles have high environmental dependence, problems such as burn density stain at low temperature and low humidity, and non-image contamination at high temperature and high humidity may occur.

On the other hand, as a method of improving the environmental dependence of toner charging, there is known a method of adding inorganic fine particles such as titanium oxide having lower electrical resistance and better charge exchangeability than silica particles. However, there is a problem that the charge distribution of the toner tends to be changed when inorganic fine particles having low electrical resistance are used.

In order to solve this problem, there is a method of controlling the resistance by surface treatment of inorganic particles having low resistance such as titanium oxide with a silane coupling agent, etc. Deterioration, the function of enhancing the original charge exchangeability is deteriorated, and there are problems such as deterioration of the toner fluidity and occurrence of blocking due to liberated aggregated particles.

In addition, unlike magnetic one-component toners, in which magnetic attraction force is a driving force, and the toner moves smoothly to the development roller, nonmagnetic one-component toner presses a blade made of metal or resin to press the development roller. Thereby controlling the adhesion thickness of the toner layer formed on the developing roller and charging the toner. Therefore, in the case of the non-magnetic one-component toner, pressure is applied to the toner, so that it is easy to block the toner on the developing roller and the blade after repeated use for a long time. There is a problem that the charge amount becomes nonuniform, the image density becomes nonuniform, and the fog phenomenon and the density unevenness occur in the image.

In order to prevent toner fusion, a method of increasing the glass transition temperature (Tg) of the binder resin contained in the toner base particles and increasing the molecular weight of the binder resin has been conventionally performed. However, this method inevitably deteriorates the fixability of the toner, and may not obtain smoothness of the fixed image, resulting in uneven image, and this method also prevents toner fusion on the developing roller in a high temperature environment. However, in the non-magnetic one-component development method in which the cleaning process is removed, especially in a low temperature environment, the remaining toner on the photoreceptor surface cannot be removed, which causes a problem of low temperature afterimages that periodically appear in the non-image area. .

Therefore, in the non-magnetic one-component developing method in which the developing roller and the photoconductor are in contact with each other, the developing roller is resistant to deformation of the developing apparatus due to environmental changes, and at the same time, it is possible to improve the low temperature afterimage phenomenon. More research is needed.

According to the present invention, the toner is smoothly supplied due to good fluidity, there is little contamination of PCR and image quality deterioration, and even though the toner layer is uniformly formed on the developing roller, no fusion occurs on the blade of the developing roller, and residual toner SUMMARY OF THE INVENTION An object of the present invention is to provide a nonmagnetic one-component toner composition capable of improving low temperature afterimages periodically appearing on non-images.

In order to achieve the above object, the present invention

a) toner base particles comprising a binder resin, a colorant and a charge control agent;

b) spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm;

c) hydrophobic silica; And

d) nonmagnetic one-component toner composition comprising fine metal oxide powder.

In addition, the present invention comprises the steps of mixing, kneading, pulverizing and classifying a binder resin, a colorant and a charge control agent to prepare toner base particles (first step); And

I) a spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm, ii) hydrophobic silica having a specific surface area of 20 to 80 m ² / g, and iii) A method for producing a nonmagnetic one-component toner comprising a step (second step) of mixing a fine metal oxide powder having an average particle diameter of 50 to 500 nm in a stirrer.

More specifically, the present invention

a) toner base particles comprising a binder resin, a colorant and a charge control agent;

b) The particle size and content of the mass average molecular weight (Mw) of 250,000 to 1.6 million, the average particle diameter of 50nm to 500nm, preferably 100nm to 300nm is 0.05 to 2.5 parts by weight based on 100 parts by weight of the toner base particles, Preferably spherical organic fine powder to add 0.1 to 2.0 parts by weight;

c) hydrophobic silica having a specific surface area of 20 to 80 m ² / g, preferably 30 to 50 m ² / g, and the content of 0.5 to 1.5 parts by weight based on 100 parts by weight of the toner base particles; And

d) The particle size and content of the average particle size of 50 nm to 500 nm, preferably 60 nm to 300 nm, the fine metal oxide powder to add 0.3 to 2.5 parts by weight, preferably 0.5 to 2.0 parts by weight based on 100 parts by weight of the toner base particles It provides a nonmagnetic one-component toner composition comprising.

More specifically, the composition comprises a) 100 parts by weight of toner base particles including 100 parts by weight of the binder resin, 3 to 20 parts by weight of the colorant and 0.5 to 5 parts by weight of the charge control agent;

b) 0.05 to 2.5 parts by weight of spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm;

c) 0.5 to 1.5 parts by weight of hydrophobic silica having a specific surface area of from 20 to 80 m ² / g; And

d) A nonmagnetic one-component toner composition comprising 0.3 to 2.5 parts by weight of fine metal oxide powder having an average particle diameter of 50 nm to 500 nm.

In addition, the present invention comprises the steps of mixing, kneading, pulverizing and classifying a binder resin, a colorant and a charge control agent to prepare toner base particles (first step); And

I) a spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm, ii) hydrophobic silica having a specific surface area of 20 to 80 m ² / g, and iii) Provided is a method for producing a nonmagnetic one-component toner, which comprises mixing a fine metal oxide powder having an average particle diameter of 50 to 500 nm in a stirrer (second step).

More specifically, the production method comprises the steps of preparing, toner base particles by mixing, kneading, pulverizing and classifying 100 parts by weight of the binder resin, 3 to 20 parts by weight of the colorant and 0.5 to 5 parts by weight of the charge control agent; And

Iv) spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm, and ii) hydrophobic silica having a specific surface area of 20 to 80 m2 / g. To 1.5 parts by weight and iii) 0.3 to 2.5 parts by weight of fine metal oxide powder having an average particle diameter of 50 to 500 nm in a stirrer (second step).

In addition, the average particle diameter of the toner base particles is not particularly limited, but is generally 5 to 25 μm, and may be manufactured by melt kneading pulverization and polymerization, and the like to prevent offset of the nonmagnetic one-component toner base particles. In order to further include a release agent.

The present inventors have a non-magnetic one-component toner composition which is resistant to deformation of the developing apparatus due to environmental changes in the non-magnetic one-component developing method in which the developing roller and the photoconductor are in contact with each other, and at the same time improve the low temperature afterimage phenomenon. During the study, spherical organic powders, hydrophobic silicas having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm on the surface of the toner base particles including the binder resin, the colorant, and the charge control agent. By producing a non-magnetic one-component toner composition containing fine metal oxide powder, the toner is smoothly supplied due to its good fluidity, the contamination and image quality of the PCR are low, and the toner layer is uniformly formed on the developing roller. No fusion occurs in the braid, and at the same time residual toner appears periodically in non-images under low temperature It confirmed that the whole residual image phenomenon can be improved, and have completed the present invention based on this.

Hereinafter, the present invention will be described in detail.

The binder resin can use a known fixing resin, and specifically, it can be obtained by polycondensation reaction of an alcohol component and a carboxylic acid component.

Examples of the alcohol component include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexane dimethanol, xylene glycol, bisphenol A, bisphenol A ethylene oxide, and bisphenol A propylene. Dihydric alcohols or alcohol derivatives such as oxides, sorbitol, and glycerin, alone or in combination, are used as the carboxylic acid component; maleic acid, fumal, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, trimellitic acid Divalent or more carboxylic acids, such as cyclopentane dicarboxylic acid, succinic anhydride, trimellitic anhydride, maleic anhydride, a carboxylic acid derivative, carboxylic anhydride, etc. can be used individually or in mixture.

Examples of the binder resin include acrylic ester polymers such as polyester, methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate, 2-ethylhexyl polyacrylate, and lauryl polyacrylate; Methacrylic acid ester polymers such as polymethyl methacrylate, polybutyl methacrylate, polyhexyl polymethacrylate, 2-ethylhexyl polymethacrylate, and lauryl polymethacrylate; Copolymers of acrylic esters with methacrylic acid esters; Copolymers of styrene monomers with acrylic or methacrylic esters; Ethylene polymers and copolymers thereof such as polyvinyl acetate, polyvinyl propionate, polyvinyl butyrate, polyethylene and polypropylene; Styrene copolymers such as styrene butadiene copolymer, styrene isoprene copolymer and styrene maleic acid copolymer; Polyvinyl ethers; Polyvinyl ketones; Polyester; Polyamides; Polyurethane; The same kind of rubber; Epoxy resins; Polyvinyl butyral rosin; Denatured rosin; A phenol resin etc. can be used individually or in mixture, and polyester is especially preferable.

The colorant is required to be included in a sufficient ratio to form a visible image of a sufficient concentration, it is generally included in a ratio of 3 to 20 parts by weight relative to 100 parts by weight of the binder resin.

Carbon black is mainly used as a black coloring agent in the said coloring agent, and the yellow, magenta, and cyan coloring agent mentioned later is used as a color coloring agent.

As a yellow colorant, a condensed nitrogen compound, an isoindolinone compound, an anthrakin compound, an azo metal complex, an allyl amide compound, etc. can be used. Specifically, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168 and the like are suitably used.

As the magenta colorant, a condensed nitrogen compound, anthrakin, quinacridone compound, a base dye lake compound, a naphthol compound, a benzimidazole compound, a thio indigo compound, a perylene compound and the like can be used. Specifically, CI Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, Particular preference is given to 185, 202, 206, 220, 221, 254.

As the cyan colorant, a copper phthalocyanine compound and derivatives thereof, an anthrakin compound, a base dye lake compound and the like can be used. Specifically, C.I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly suitable.

Such colorants may be used alone or in admixture of two or more thereof, and may also be used in solid solution, but are not limited thereto. Colorants of the present invention are selected in terms of characteristics such as color, saturation, lightness, weather resistance, OHP transparency, dispersibility in toner, and the like.

The charge control agent may be a metal azo dye, a salicylic acid compound, etc., when the charge is negative charge, nigrosine dye, quaternary ammonium salt, etc. may be used when positive charge. Although content in a toner of a charge control agent is not specifically limited, Generally 0.5-5 weight part is preferable with respect to 100 weight part of binder resins.

When only hydrophobic silica is used for the non-magnetic one-component toner, it shows a very good result in terms of fluidity. However, in the present invention, since the toner is fused and the improvement effect is not remarkable in terms of contamination of PCR when a large amount of output is produced for a long time, Spherical organic fine powder having an average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm is added together with the hydrophobic silica.

As in the present invention, when the spherical organic fine powder is used together with silica, the charging behavior of the toner is influenced by the spherical organic powder and the silica surrounding the organic powder on the surface of the toner particles, and between the sleeve and the charging blade during charging ( By reducing the frictional resistance received by the toner in the charging blade, it is possible to obtain a long-term stable image by preventing the formation of melt or solid adhesion between the toner on the charging blade.

The term spherical as described herein refers to a case where the average value of circularity (R) is 0.92 or more when expressed by the following equation.

R = L0 / L1 --- (I)

In the above formula, the unit of L1 is nm and refers to the perimeter of the projected image of particles of the average particle diameter of the organic fine powder to be measured, and the unit of L0 is nm and the projection image of the organic fine powder to be measured Perimeter of circle having the same area as the projected area of particles.

Therefore, when R = 1.0, it is a case where a circle becomes round and can be said to be a perfect spherical form.

The spherical organic fine powder has a mass average molecular weight (Mw) of 250,000 to 1.6 million, preferably an average particle diameter of 50nm to 500nm, more preferably 100 to 300nm. If the mass average molecular weight is less than 250,000, contamination occurs on the fixing roller due to the temperature of the fixing unit. If the mass average molecular weight is 1.6 million or more, frictional charging with the toner charging restricting member is prevented, resulting in background contamination and image density reduction. . In addition, when the average particle diameter is less than 50 nm, there is a problem in that toner fusion occurs due to insufficient organic fine powder on the surface of the toner base particles, and when the average particle diameter exceeds 500 nm, the organic fine powder is separated from the surface of the toner base particles. There is a problem that the fixing failure of the toner particles occurs.

The spherical organic fine powder is preferably contained in an amount of 0.05 to 2.5 parts by weight, more preferably 0.1 to 2.0 parts by weight based on 100 parts by weight of the toner base particles. If the content is less than 0.05 parts by weight, the effect is insignificant. If it is more than 2.5 parts by weight, too much spherical organic fine powder present on the surface of the toner particles may cause contamination problems such as PCR contamination, drum contamination, and degradation of transfer efficiency. Is caused.

The spherical organic fine powder has a polymer structure and can be produced from the following monomers. Examples of the monomers include styrenes such as styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene or nonyl styrene; Vinyl halides such as vinyl chloride or vinyl fluoride; Vinyl esters such as vinyl acetate or vinyl benzoate; Methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate or phenyl acrylate; Acrylic acid derivatives such as acrylonitrile or methacrylonitrile; Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or phenyl acrylate; Tetrafluoroethylene; Or 1,1-difluoroethylene or the like can be used alone or in combination. In addition, the monomer may be used by mixing with a styrene resin, an epoxy resin polyester resin or a polyurethane resin.

The hydrophobic silica has a specific surface area of 20 to 80 m ² / g, preferably 30 to 50 m ² / g, and has an effect of preventing the toner from fusing to the blade. When the specific surface area of the silica is less than 20 m ² / g, the toner is easy to block on the blade, and streaks are formed on the print image. When the silica exceeds 80 m ² / g, the hydrophobic silica is buried on the surface of the toner particles. The toner is fused to the blade and the durability is lost. The hydrophobic silica should be used together with the spherical organic fine powder to prevent the toner from fusing to the blade.

The specific surface area of the hydrophobic silica means a specific surface area measured by the BET method, and the value can be measured by a commercially available high precision automatic gas adsorption device or the like. Such a measuring device obtains the BET specific surface area (m ² / g) by measuring the amount of gas adsorption required to form a monolayer on the surface of hydrophobic silica particles using an inert gas, especially nitrogen gas, as the adsorption gas.

The amount of adhesion of the hydrophobic silica to the toner particle surface is preferably 0.5 to 1.5 parts by weight based on 100 parts by weight of the toner base particles. If the adhesion amount of silica is less than 0.5 parts by weight, the effect of imparting improved fluidity to the toner is insufficient, causing contamination of the PCR, causing stains on the developed image or fusion of the toner to the blades. Fixability is reduced by the influence of the silica remaining after adhesion.

For hydrophobization treatment of the silica particles, a surface treatment for applying or adhering a silane coupling agent or silicone oil or the like to the silica particles may be used.

The silane coupling agent is dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, arylphenyldichlorosilane, benzyldimethylchlorosilane, bromine methyldimethylchlorosilane, P-chlorophenyltrichlorosilane, 3-chloropropyltrimethoxy , Vinyltriethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, hexamethylenedisiragen and the like can be used.

The silicone oil has a viscosity of 50 to 10,000 cps (centipoises) at 25 ℃, dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, alcohol modified silicone oil, amino modified silicone oil , Epoxy modified silicone oil, epoxy polyether modified silicone oil, phenol modified silicone oil, carboxy modified silicone oil, mercapto modified silicone oil and the like can be used.

The hydrophobization treatment with silicone oil is not particularly limited as long as the silicone oil is adsorbed on the surface of the inorganic powder. For example, the silicone oil is diluted in a solvent and sprayed while continuing to stir with the silica itself in a mixing bath. The method of heat-drying for a predetermined time in a mixing tank is mentioned.

As a method of attaching the hydrophobic silica to the toner particles, a general agitator such as a turbine type agitator, a Henschel mixer, a super mixer, or a device called a surface reformer ("Nara Hybridization System" of Nara Machinery Co., Ltd.) may be used. There is a way to use it. Further, the hydrophobic silica on the surface of the toner particles may be attached to the toner particles in a weak adhesion state, or the hydrophobic silica may be fixed to the surface of the toner particles in a buried state.

The fine metal oxide powder has an average particle diameter of 50 to 500 nm, preferably 60 to 300 nm. When the average particle diameter of the fine metal oxide powder is 50 nm or less or 500 nm or more, the improvement effect in terms of fluidity and PCR contamination is reduced. The fine metal oxide powder should be used simultaneously with the spherical organic fine powder and the hydrophobic silica to exhibit an improvement effect in terms of fluidity and PCR contamination.

The fine metal oxide powder may be titanium dioxide, aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide, and the like, and among these, titanium dioxide is preferable in view of the degree of modification and availability. .

The adhesion amount of the fine metal oxide powder is preferably 0.3 to 2.5 parts by weight, more preferably 0.5 to 2 parts by weight based on 100 parts by weight of the toner base particles. If the amount of adhesion is 0.3 parts by weight or less, there is no PCR contamination improvement effect, and when 2.5 parts by weight or more, poor fixability occurs.

In general, the release agent may be a low molecular weight polyethylene wax or polypropylene wax, low molecular weight olefin resin, and the like, in addition to the metal salt fatty acid may be used. The low molecular weight olefin resin may be polypropylene, polyethylene, propylene ethylene copolymer or the like, and the fatty acid may be a natural fatty acid or synthetic fatty acid having 4 to 40 carbon atoms, and may be either saturated or unsaturated, and a hydroxyl group in the structure. , Aldehyde group or epoxy group, and examples thereof include caproic acid, caprylic acid, capuric acid, lyric acid, myristic acid, milist oleic acid, parmitic acid, palmito oleic acid, stearic acid, oleic acid, linolenic acid, arakin Acids, behenic acid, elcaic acid, monthenic acid, isostearic acid, epoxy stearic acid, or the like can be used. The release agent is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the binder resin, and particularly preferably polypropylene.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

<Example 1>

1) Preparation of Toner Base Particles

Each raw material blended in the composition ratio of Table 1 was mixed with a Henschel mixer, melt kneaded at a temperature of 155 ° C. in a biaxial melt kneader, pulverized with a jet mill grinder, and classified in a wind classifier to give a volume. Toner base particles having an average particle diameter of 8.9 mu m were obtained.

division ingredient Compounding ratio (part by weight) Binding resin Polyester resin 100 coloring agent Carbon black 10 Antistatic agent Metal Azo Salts 3 Release agent Low molecular weight polypropylene 3

2) Preparation of nonmagnetic one-component toner composition

0.1 parts by weight of polystyrene butyl methacrylate (polystryene-n-butylmethacrylate, PS / BMA) having a mass average molecular weight of 250,000 and an average particle diameter of 500,000 with respect to 100 parts by weight of the prepared toner base particles 0.5 parts by weight of hydrophobic silica having a specific surface area of 60 m ² / g with hydrophobic silica and fine powder of metal oxide with an average particle diameter of 100 nm and 1.0 parts by weight of titanium oxide using a Henschel mixer for 5 minutes, followed by mixing and mixing The surface was coated to prepare a nonmagnetic one-component toner.

<Examples 2 to 88 and Comparative Examples 1 to 20>

As shown in Table 2, Table 3, Table 4 and Table 5, except that the content of the polystyrene butyl methacrylate organic fine powder, hydrophobic silica and fine metal oxide powder was used in the same manner as in Example 1 It was. The toner compositions of the examples are shown in Tables 3 and 4, and the toner compositions of the comparative examples are shown in Table 5.

division Mass average molecular weight (Mw, only) Average particle size (nm) PS / BMA A 25 50 PS / BMA B 25 200 PS / BMA C 25 500 PS / BMA D 80 50 PS / BMA E 80 200 PS / BMA F 80 500 PS / BMA G 160 50 PS / BMA H 160 200 PS / BMA I 160 500 PS / BMA J 15 200 PS / BMA K 200 200 PS / BMA L 80 40 PS / BMA M 80 600

<Example> division Organic fine powder (parts by weight) Hydrophobic silica (parts by weight) Titanium oxide (parts by weight) 2 PS / BMA A, 0.05 0.5 1.0 3 PS / BMA A, 1.5 0.5 1.0 4 PS / BMA A, 2.5 0.5 1.0 5 PS / BMA A, 0.05 1.0 1.0 6 PS / BMA A, 1.5 1.0 1.0 7 PS / BMA A, 2.5 1.0 1.0 8 PS / BMA A, 0.05 1.5 1.0 9 PS / BMA A, 1.5 1.5 1.0 10 PS / BMA A, 2.5 1.5 1.0 11 PS / BMA B, 0.05 0.5 1.0 12 PS / BMA B, 1.5 0.5 1.0 13 PS / BMA B, 2.5 0.5 1.0 14 PS / BMA B, 0.05 1.0 1.0 15 PS / BMA B, 1.5 1.0 1.0 16 PS / BMA B, 2.5 1.0 1.0 17 PS / BMA B, 0.05 1.5 1.0 18 PS / BMA B, 1.5 1.5 1.0 19 PS / BMA B, 2.5 1.5 1.0 20 PS / BMA C, 0.05 0.5 1.0 21 PS / BMA C, 1.5 0.5 1.0 22 PS / BMA C, 2.5 0.5 1.0 23 PS / BMA C, 0.05 1.0 1.0 24 PS / BMA C, 1.5 1.0 1.0 25 PS / BMA C, 2.5 1.0 1.0 26 PS / BMA C, 0.05 1.5 1.0 27 PS / BMA C, 1.5 1.5 1.0 28 PS / BMA C, 2.5 1.5 1.0 29 PS / BMA D, 0.05 0.5 1.0 30 PS / BMA D, 1.5 0.5 1.0 31 PS / BMA D, 2.5 0.5 1.0 32 PS / BMA D, 0.05 1.0 1.0 33 PS / BMA D, 1.5 1.0 1.0 34 PS / BMA D, 2.5 1.0 1.0 35 PS / BMA D, 0.05 1.5 1.0 36 PS / BMA D, 1.5 1.5 1.0 37 PS / BMA D, 2.5 1.5 1.0 38 PS / BMA E, 0.05 0.5 1.0 39 PS / BMA E, 1.5 0.5 1.0 40 PS / BMA E, 2.5 0.5 1.0 41 PS / BMA E, 0.05 1.0 1.0 42 PS / BMA E, 1.5 1.0 1.0 43 PS / BMA E, 2.5 1.0 1.0 44 PS / BMA E, 0.05 1.5 1.0 45 PS / BMA E, 1.5 1.5 1.0 46 PS / BMA E, 2.5 1.5 1.0 47 PS / BMA F, 0.05 0.5 1.0 48 PS / BMA F, 1.5 0.5 1.0 49 PS / BMA F, 2.5 0.5 1.0

<Example> Organic fine powder (parts by weight) Hydrophobic silica (parts by weight) Titanium oxide (parts by weight) 50 PS / BMA F, 0.05 1.0 1.0 51 PS / BMA F, 1.5 1.0 1.0 52 PS / BMA F, 2.5 1.0 1.0 53 PS / BMA F, 0.05 1.5 1.0 54 PS / BMA F, 1.5 1.5 1.0 55 PS / BMA F, 2.5 1.5 1.0 56 PS / BMA G, 0.05 0.5 1.0 57 PS / BMA G, 1.5 0.5 1.0 58 PS / BMA G, 2.5 0.5 1.0 59 PS / BMA G, 0.05 1.0 1.0 60 PS / BMA G, 1.5 1.0 1.0 61 PS / BMA G, 2.5 1.0 1.0 62 PS / BMA G, 0.05 1.5 1.0 63 PS / BMA G, 1.5 1.5 1.0 64 PS / BMA G, 2.5 1.5 1.0 65 PS / BMA H, 0.05 0.5 1.0 66 PS / BMA H, 1.5 0.5 1.0 67 PS / BMA H, 2.5 0.5 1.0 68 PS / BMA H, 0.05 1.0 1.0 69 PS / BMA H, 1.5 1.0 1.0 70 PS / BMA H, 2.5 1.0 1.0 71 PS / BMA H, 0.05 1.5 1.0 72 PS / BMA H, 1.5 1.5 1.0 73 PS / BMA H, 2.5 1.5 1.0 74 PS / BMA I, 0.05 0.5 1.0 75 PS / BMA I, 1.5 0.5 1.0 76 PS / BMA I, 2.5 0.5 1.0 77 PS / BMA I, 0.05 1.0 1.0 78 PS / BMA I, 1.5 1.0 1.0 79 PS / BMA I, 2.5 1.0 1.0 80 PS / BMA I, 0.05 1.5 1.0 81 PS / BMA I, 1.5 1.5 1.0 82 PS / BMA I, 2.5 1.5 1.0 83 PS / BMA E, 1.5 0.5 0.3 84 PS / BMA E, 1.5 0.5 2.5 85 PS / BMA E, 1.5 1.0 0.3 86 PS / BMA E, 1.5 1.0 2.5 87 PS / BMA E, 1.5 1.5 0.3 88 PS / BMA E, 1.5 1.5 2.5

Comparative Example division Organic fine powder (jungnangbu) Hydrophobic Silica (Powder) Titanium oxide (parts by weight) One PS / BMA E, 1.5 1.0 0.2 2 PS / BMA E, 1.5 1.0 2.6 3 PS / BMA E, 1.5 0.4 1.0 4 PS / BMA E, 1.5 1.6 1.0 5 - 1.0 1.0 6 - 1.0 1.0 7 PS / BMA E, 1.5 - 1.0 8 PS / BMA E, 1.5 - 1.0 9 PS / BMA E, 1.5 1.0 - 10 PS / BMA E, 1.5 1.0 - 11 PS / BMA E, 0.03 0.5 1.0 12 PS / BMA E, 3.0 0.5 1.0 13 PS / BMA E, 0.03 1.0 1.0 14 PS / BMA E, 3.0 1.0 1.0 15 PS / BMA E, 0.03 1.5 1.0 16 PS / BMA E, 3.0 1.5 1.0 17 PS / BMA J 1.5 0.5 1.0 18 PS / BMA K 1.5 0.5 1.0 19 PS / BMA L 1.5 0.5 1.0 20 PS / BMA M 1.5 0.5 1.0

<Example 89>

PMMA powder of polymethyl methacrylate instead of PS / BMA was used in a substantially same manner as in Example 1 using 0.1 μm in size and a mass average molecular weight (Mw) of 1.5 million parts by weight instead of PS / BMA. A nonmagnetic one-component toner was prepared.

Comparative Example 21

Instead of the spherical organic fine powder PS / BMA used in Example 89, the size of the organic fine powder (St / BA / MMA powder) consisting of styrene-butylacrylate-methacrylic acid (non-spherical: R = 0.54) Toner was prepared in substantially the same manner as in Example 1, except that 0.15 µm and a mass average molecular weight (Mw) were used by 1.5 parts by weight instead of 600,000 by PS / BMA.

Experimental Example 1

Low temperature and low humidity using a contactless, nonmagnetic one-component developing method printer (ML5300, Samsung Electronics Co., Ltd.) commercially available for the nonmagnetic one-component toner compositions prepared in Examples 1 to 89 and Comparative Examples 1 to 21. (5 degreeC, 20% RH) and up to 5,000 sheets were printed in the environment of normal temperature normal humidity (20 degreeC, 55% RH), and toner physical property was evaluated as follows.

1. Low temperature afterimage phenomenon

At low temperature and low humidity (5 ° C, 20% RH), it was visually observed whether or not the pattern of the image part appeared in the non-image part by printing an image having a certain pattern on a predetermined number of plain papers.

Low temperature afterimage (good): No pattern on non-image.

Low temperature afterimage occurrence (poor): The pattern of the image portion is printed on the non-image portion.

2. Toner fusion

After printing a predetermined number of sheets, the toner was fused to the developing blade through the printing of a black solid image, which interrupted the supply of the toner to the developing drum and observed whether streaks such as nails were generated on the printed image.

No toner fusion (good): There are no streaks.

Toner Fusion (Defect): Streaks occur in solid patterns.

3. Fixation Characteristics

After printing a predetermined number of sheets, it was observed whether the same pattern due to a fixing failure occurred in the non-image portion in the image output through the fixing portion through the printing of an image having a certain pattern.

No fixation failure (good): The same pattern does not occur on non-images.

Bad fixation (bad): The same pattern is generated in the non-image area.

There was no low temperature afterimage, toner fusion, and fixing failure for Examples 1 to 89. Also, in the case of Comparative Examples 1 to 121, the results shown in Table 6 below were obtained.

division Afterimage Toner Fusion Settling failure Comparative Example 1 none Occur none Comparative Example 2 none none Bad Comparative Example 3 Occur none Bad Comparative Example 4 Occur Occur none Comparative Example 5 none Occur none Comparative Example 6 Occur Occur none Comparative Example 7 none Occur none Comparative Example 8 none none Bad Comparative Example 9 Occur none none Comparative Example 10 none Occur none Comparative Example 11 Occur none Bad Comparative Example 12 none Occur none Comparative Example 13 Occur none Bad Comparative Example 14 Occur none none Comparative Example 15 none Occur Bad Comparative Example 16 Occur Occur none Comparative Example 17 Occur Occur none Comparative Example 18 none none Bad Comparative Example 19 Occur Occur none Comparative Example 20 none none Bad Comparative Example 21 Occur Occur none

Therefore, it was confirmed that the nonmagnetic one-component toner compositions of Examples 1 to 89 according to the present invention had excellent low temperature afterimage, toner fusion and fixing characteristics as compared with Comparative Examples 1 to 21. In addition, in Comparative Example 21, unlike the case of using the spherical organic fine powder, it was confirmed that the toner fusion occurs on the blade due to the aggregation phenomenon between the toner occurs. In addition, PCR contamination was confirmed to increase.

As described above, in the nonmagnetic one-component toner according to the present invention, in the nonmagnetic one-component developing method in which the developing roller and the photoconductor are in contact with each other, the toner is smoothly supplied, and the contamination of the PCR and the deterioration of image quality are low. In addition, although the toner layer is uniformly formed on the developing roller, no fusion occurs on the blades of the developing roller, and at the same time, the low temperature afterimage phenomenon in which residual toner periodically appears in the non-image under the low temperature environment can be improved. It can be usefully used for an image output apparatus adopting a nonmagnetic one-component developing method in contact.

Claims (15)

delete a) 100 parts by weight of toner base particles including 100 parts by weight of the binder resin, 3 to 20 parts by weight of colorant and 0.5 to 5 parts by weight of charge control agent; b) 0.05 to 2.5 parts by weight of spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm; c) 0.5 to 1.5 parts by weight of hydrophobic silica having a specific surface area of from 20 to 80 m ² / g; And d) a nonmagnetic one-component toner composition comprising 0.3 to 2.5 parts by weight of fine metal oxide powder having an average particle diameter of 50 nm to 500 nm. The spherical organic fine powder of b) is styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene or nonyl styrene; Vinyl halides of vinyl chloride or vinyl fluoride; Vinyl esters of vinyl acetate or vinyl benzoate; Methacrylates of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate or phenyl acrylate; Acrylic acid derivatives of acrylonitrile or methacrylonitrile; Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or phenyl acrylate; Tetrafluoroethylene; A nonmagnetic one-component toner composition, characterized in that the polymer is prepared from monomers of 1,1-difluoroethylene or a mixture thereof. 3. The nonmagnetic one-component toner composition according to claim 2, wherein the toner base particles of a) further comprise 0.05 to 5 parts by weight of a release agent. delete 3. The nonmagnetic one-component toner composition according to claim 2, wherein the hydrophobic silica of c) is hydrophobized with a silane coupling agent or silicone oil. 6. The nonmagnetic one-component toner composition according to claim 5, wherein the silicone oil has a viscosity of 50 to 10,000 cps at 25 ° C. 3. The non-magnetic work according to claim 2, wherein the fine metal oxide powder of d) is at least one selected from the group consisting of titanium dioxide, aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide and tin oxide. Component Toner Composition. Mixing, kneading, pulverizing, and classifying a binder resin, a colorant, and a charge control agent to prepare toner base particles (first step); And I) a spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm, ii) hydrophobic silica having a specific surface area of 20 to 80 m ² / g, and iii) A method for producing a nonmagnetic one-component toner, comprising the step of mixing a fine metal oxide powder having an average particle diameter of 50 to 500 nm in a stirrer (second step). The method of claim 8, Mixing, kneading, pulverizing and classifying 100 parts by weight of the binder resin, 3 to 20 parts by weight of the colorant and 0.5 to 5 parts by weight of the charge control agent to prepare toner base particles (first step); And Iv) spherical organic fine powder having a mass average molecular weight (Mw) of 250,000 to 1.6 million and an average particle diameter of 50 nm to 500 nm, and ii) hydrophobic silica having a specific surface area of 20 to 80 m ² / g. 0.5 to 1.5 parts by weight and iii) mixing 0.3 to 2.5 parts by weight of fine metal oxide powder having an average particle diameter of 50 to 500 nm in a stirrer (second step). 10. The non-magnetic separator according to claim 8 or 9, wherein the mixing of the first step is performed in a Henschel mixer, kneading in a twin screw melt kneader, grinding in a jet mill grinder, and classification in a wind classifier. Method for producing a one-component toner. 10. The method of manufacturing a nonmagnetic one-component toner according to claim 8 or 9, further comprising 0.05 to 5 parts by weight of a release agent to the toner base particles of the first step. 10. The method of claim 8 or 9, wherein the spherical organic fine powder of the second step is styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene or nonyl styrene; Vinyl halides of vinyl chloride or vinyl fluoride; Vinyl esters of vinyl acetate or vinyl benzoate; Methacrylates of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate or phenyl acrylate; Acrylic acid derivatives of acrylonitrile or methacrylonitrile; Acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or phenyl acrylate; Tetrafluoroethylene; A method for producing a nonmagnetic one-component toner, characterized in that the polymer is prepared from monomers made of 1,1-difluoroethylene or a mixture thereof. The method of manufacturing a nonmagnetic one-component toner according to claim 8 or 9, wherein the hydrophobic silica of the second step is hydrophobized with a silane coupling agent or a silicone oil. The method of claim 13, wherein the silicone oil has a viscosity of 50 to 10,000 cps at 25 ° C. The fine metal oxide powder of the second step is at least one selected from the group consisting of titanium dioxide, aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide and tin oxide. A method for producing a nonmagnetic one-component toner.