KR100713780B1 - Color toner for non-magnetic mono-component system for increasing printing quality and a method for preparing the same - Google Patents

Abstract

The present invention relates to a nonmagnetic one-component color toner capable of improving print quality and a method of manufacturing the same. More specifically, after preparing a coating organic powder in which two spherical organic powders are coated on each other's surface, first coating the surface of the toner base particles, and coating coated inorganic powder with silica and titanium dioxide mixed therein The secondary coating provides a non-magnetic one-component color toner in which the toner base particles are multi-coated with an organic powder and an inorganic powder, and a manufacturing method thereof.

The manufactured color toner has a narrow charge distribution and high conductivity, which not only has excellent image density and transfer efficiency, but also improves long-term reliability and prevents contamination of photosensitive drums and charging rollers. It is preferably applied to a printer or the like.

Non-magnetic one-component color toner, organic powder, silica, high conductivity, antistatic property, high image density, high thermal efficiency, long-term reliability, PCR contamination

Description

Non-magnetic one-component color toner that can improve print quality and its manufacturing method {COLOR TONER FOR NON-MAGNETIC MONO-COMPONENT SYSTEM FOR INCREASING PRINTING QUALITY AND A METHOD FOR PREPARING THE SAME}

1 is a cross-sectional view showing the structure of a nonmagnetic one-component color toner according to the present invention.

Figure 2 is a scanning electron microscope (SEM) photograph showing the surface state of the particles obtained after the primary coating on the toner base particles according to an embodiment of the present invention.

3 is a scanning electron microscope (SEM) photograph showing a state in which the toner base particles are coated between the organic powders of the particles obtained after the first coating on the toner base particles.

Figure 4 is a scanning electron microscope (SEM) photograph showing the surface state of the particles obtained by the second coating after the first coating, according to an embodiment of the present invention.

FIG. 5 is a scanning electron microscope (SEM) photograph showing a state in which inorganic particles of the particles obtained by the second coating and the second coating are coated according to an embodiment of the present invention.

The present invention relates to a nonmagnetic one-component color toner having a narrow charge distribution, high conductivity, excellent image density and transfer efficiency, and improved long-term reliability, and a manufacturing method thereof.

In recent years, color printing is rapidly progressing with digitization, and researches on an image forming method for realizing high quality and high quality images and improvement methods of toner used at this time are actively conducted with the spread of digital devices.

In general, toner is manufactured by kneading pulverization, suspension polymerization, emulsification polymerization, emulsion aggregation, and the like using a binder resin, a colorant, a charge control agent, a release agent, and the like as raw materials.

These toner particles are developed by the triboelectric charging method and retain positive or negative charges depending on the polarity of the developed electrostatic latent image. At this time, the charging performance of the toner is also influenced by the internal blending as described above. However, since the toner is more affected by the additive added to the surface, the charging performance is controlled by the blending of the additive and the addition method.

In general, additives used in toner are used to reduce the resistance associated with the rotating portion that rotates the developing sleeve in the toner supply portion in the developing process, and to suppress the toner from fusing to a charging blade or the like and agglomeration of the toners. In addition, it not only serves to obtain a uniform and stable toner layer with low torque, but also has a specific range of frictional charging characteristics, stabilizes charging characteristics and improves charge retention. However, when additives are not uniformly added to the surface of the toner, the charging properties of the particles are different from each other, so that a uniform image cannot be obtained. In addition, even when the additive is uniformly coated on the surface of the toner, in the non-magnetic one-component toner, the pressure applied to the toner as the printing proceeds, the toner-toner, the toner-charging blade, or the toner-sleeve Agglomeration may occur, in which case the image becomes blurred and uneven in the long term. Therefore, in order to solve this problem, it is very important to select the appropriate additives and design the content and particle size.

In particular, with the recent rapid development of digital devices, high quality, high speed, and colorization are rapidly progressing, so that a toner having higher and accurate transfer performance and stable charging performance in the long term is required.

The present invention for solving the above problems has a narrow charge distribution and high conductivity, not only excellent in image density and transfer efficiency, but also significantly improves charge retention, and has excellent long-term reliability, and contaminates the photosensitive drum and the charging roller. An object of the present invention is to provide a non-magnetic one-component color toner that does not occur and a method of manufacturing the same.

In order to achieve the above object, the present invention includes a primary coating layer and a secondary coating layer formed on the surface of the toner base particles on the surface of the toner base particles, the primary coating layer is a coating in which two organic powders are coated on the surface of each other An organic powder is contained, and the secondary coating layer provides a color toner for a nonmagnetic one-component printing system containing a coated inorganic powder in which silica and titanium dioxide are coated on each other's surface.

In addition, the present invention

 a) mixing two spherical organic powders and coating them on the surface of each other to prepare a coated organic powder;

b) coating the coated organic powder on the surface of the toner base particles to prepare toner base particles having a first coating layer;

c) mixing silica and titanium dioxide and coating the surface of each other to prepare a coated inorganic powder; And

d) coating the coated inorganic powder with toner base particles on the first coating layer of step b) to form a second coating layer;

It provides a method for producing a nonmagnetic one-component color toner comprising a.

In this case, the non-magnetic one-component color toner is 0.1 to 2.0 parts by weight of each spherical organic powder having an average particle size of 0.1 μm to 1.8 μm and silica powder having an average particle size of 3 nm to 40 nm based on 100 parts by weight of the toner base particles. It is preferable to include 1.0 to 4.0 parts by weight, and 0.1 to 2.0 parts by weight of titanium dioxide powder having an average particle diameter of 80 to 200 nm.

The thickness of the first coating layer is 10 nm to 200 nm, the second coating layer has a thickness of 3 nm to 200 nm.

In addition, the toner base particles preferably include a binder resin, a colorant, and a charge control agent.

Coating of the color toner is preferably performed by using one kind of mixer selected from the group consisting of a Henschel mixer, a turbine type stirrer, a super mixer, and a hybridizer.

Hereinafter, the present invention will be described in more detail.

The properties of the additives present on the surface of the toner particles are greatly related to the charge performance and charge retention of the toner.

1 is a cross-sectional view showing the structure of a nonmagnetic one-component color toner according to the present invention. Referring to FIG. 1, the color toner according to the present invention includes a first coating layer 20 and a second coating layer 30 formed on the surface of the toner base particles 10, wherein the first coating layer has two organic powders coated on the surface of each other. A coating organic powder is contained, and the second coating layer contains a coating inorganic powder in which silica and titanium dioxide are coated on each other's surface.

The toner base particles 10 are not particularly limited in the present invention. The toner base particles 10 include binder resins, colorants, and charge control agents as essential components, and include one of kneading milling method, suspension polymerization method, emulsification polymerization method, and emulsion aggregate method. Purchased and used directly or commercially prepared by the method of, has a spherical or amorphous particle form. In this case, the toner base particles may further include one or more other additives such as a fluidity accelerator and a release agent, as necessary. For example, the toner base particles 10 may include 90 to 120 parts by weight of a binder, 0.5 to 20 parts by weight of a colorant, and 0.1 to 10 parts by weight of a charge control agent, and 0.1 to 10 parts by weight of a fluidity accelerator or a release agent, respectively.

Binder resins that can be used include acrylic acid ester polymers such as polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, 2-ethylhexyl polyacrylate, or lauryl polyacrylate; Methacrylic acid ester polymers such as polymethyl methacrylate, polybutyl methacrylate, polyhexyl methacrylate, polyethyl methacrylate 2-ethyl hexyl, or 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 or polypropylene; Styrene-based copolymers such as styrene butadiene copolymer, styrene isoprene copolymer, or styrene maleic acid copolymer; Polystyrene-based resins; Polyvinyl ether resins; Polyvinyl ketone resins; Polyester-based resins; Polyurethane-based resins; Epoxy resins; Or silicone resin etc. are used individually or in mixture.

Preferably the polymer is a polystyrene resin, polyester resin, polyethylene resin, polypropylene resin, alkyl styrene acrylate, alkyl styrene methacrylate copolymer, styrene acrylonitrile copolymer of C1 to C18, styrene butadiene air At least one selected from the group consisting of copolymers and styrene maleic acid copolymers is possible.

Colorants are used to form a visual image of sufficient concentration, and magnetic powders, dyes and pigments are commonly used which may represent cyan, magenta, yellow and black used in color printing. In this case, carbon black is mainly used as the black colorant.

Typically, yellow colorants include condensed nitrogen compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes or allyl amide compounds, which are directly synthesized or commercially available. For example, as the yellow colorant CI pigment yellow 97, CI pigment yellow 12, CI pigment yellow 17, CI pigment yellow 14, CI pigment yellow 13, CI pigment yellow 16, CI pigment yellow 81, CI pigment yellow 126, CI pigment yellow 127, etc. are used.

As magenta colorants, condensed nitrogen compounds, anthraquinones, quinacridone compounds, base dye lake compounds, naphthol compounds, benzoimidazole compounds, thioindigo compounds, or perylene compounds are used. Rosebengal, C.I. Pigment red 48: 1, C.I. pigment, red 48: 4, C.I. Pigment red 122, C.I. pigment, red 57: 1 and C.I. pigment, red 257, and the like.

As the cyan colorant, a phthalocyanine compound and derivatives thereof, an anthraquinone compound, or a base dye lake compound, etc. are used. Phthalocyanine blue, lamp black, CI pigment blue 9, CI pigment blue 15, CI pigment blue 15: 1 and CI pigment blue 15: 3 etc. are possible.

As the charge control agent, a metal azo dye, a salicylic acid compound, etc. may be used as the auxiliary charge control agent, and a nigrosine dye, a quaternary ammonium salt, or the like may be used as the antistatic charge control agent.

Additional flow promoters include SiO ₂ , TiO ₂ , MgO, Al ₂ O ₃ , ZnO, Fe ₂ O ₃ , CaO with hydrophobization treatment such as hexamethyldisilazane, dimethyl dichlorosilane, octyl trimethoxy silane, etc. , BaSO ₄ , CeO ₂ , K ₂ O, Na ₂ O, ZrO ₂ , CaOSiO ₂ , and K ₂ O.SiO ₂ , Al ₂ O ₃ ㆍ SiO ₂ It is suitably used within the range.

In addition, the release agent is used to prevent off-set of the toner base particles 10, and various waxes and low molecular weight olefin resins commonly used in this field are possible. Typically, the olefin resin is preferably polypropylene, polyethylene, propylene ethylene copolymer or the like.

Particularly, in the present invention, the coating organic powder and the coating inorganic powder are sequentially coated on the surface of the toner base particles 10 in order to improve various characteristics as toners on the toner base particles 10 having the composition described above. The coating layer 20 and the second coating layer 30 are formed.

The coating organic powder present in the first coating layer 20 contacts the surface of the charging blade during charging of the photosensitive drum to reduce frictional resistance, thereby lowering the frictional resistance received by the toner between the sleeve and the charging blade. It is possible to obtain a long-term stable image by preventing solid deposition of toner particles in the process. In addition, the coating inorganic powder forming the subsequent second coating layer 30 not only adheres well to the toner base particles, but also lowers the adhesion force between the toner particles to maintain charging characteristics.

In order to perform this role, the first coating layer 20 mixes two kinds of organic powders of different sizes with each other to prepare a coating organic powder, and then coats the surface of the toner base particles.

As the coating organic powder forming the first coating layer 20 uses different sizes, as shown in FIG. 1, a small spherical organic powder effectively concave the concave portion of the surface of the amorphous toner base particles. Fill it. As a result, the amorphous toner base particles exhibit the same behavior as the toner base particles formed from the spherical particles having a uniform surface, and each toner particle including the same has a uniform surface charging characteristic and thus a uniform toner particle layer on the developing sleeve. By forming a uniform image in the long term, and improve the transfer efficiency. However, when one type of organic powder is used as in the prior art, the surface of the final manufactured toner particles may be uneven because the concave portions of various sizes and shapes of the toner base particles cannot be effectively filled to obtain uniform charging characteristics. Can't.

The two organic powders forming the first coating layer 20 may be mixed with each other having a number average particle size of 0.1 μm to 1.8 μm, but varying the size of the particle size. If the particle size of the organic powder is larger than 1.8 μm, adhesion to the surface of the toner particles is greatly degraded, and thus, uniform charging characteristics of the spherical particles can not be effectively attached to the concave portion of the surface of the toner particle, which is originally desired. You will not be able to achieve the effect. On the contrary, if it is lower than 0.1 μm, the frictional resistance with the charging blade may not be sufficiently lowered, and the concave portion may not be sufficiently filled on the surface of the amorphous toner particles, which is the intended purpose, and it may be difficult to achieve spherical effects. The small particles are difficult to control so that it is difficult to enter the desired position of the toner base particles 10, and thus is appropriately selected within the above range.

The thickness of the first coating layer 20 has a thickness of at least 10 nm to 200 nm. In particular, the size of the toner particles on which the first coating layer 20 of the present invention is formed is concave instead of uniformly coating the surface of the toner base particles 10 by the organic powder forming the first coating layer 20 sequentially. The average size (number average) of the toner particles as a whole may be partially different when compared with the size of the original toner base particles 10, but when the total average, the toner particles have a large influence on the size of the toner particles. Not crazy

The content of the spherical coated organic powder is determined in consideration of adhesion to the surface of the toner and adhesion to the second coating layer 20, and preferably 0.2 to 4.0 parts by weight based on 100 parts by weight of the toner base particles. Each organic powder is used in 0.1 to 2.0 parts by weight. If the content of the coated organic powder is less than 0.2 parts by weight, it is difficult to expect the effect obtained by adding the organic powder. If the content of the coated organic powder exceeds 4.0 parts by weight, the uniform charging characteristics may not be obtained and the charging roller or drum may be contaminated and transferred. Significantly lower the efficiency.

The organic powder to be used may be a polymer commonly used in this field, and typically, styrenes such as styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene, and nonyl styrene; Vinyl halides selected from the group consisting of vinyl chloride and vinyl fluoride; Vinyl esters of vinyl acetate and vinyl benzoate; Methacrylates selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and phenyl acrylate; Acrylic acid derivatives selected from the group consisting of acrylonitrile and methacrylonitrile; Acrylates selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate and phenyl acrylate; Tetrafluoroethylene; And a single or copolymer consisting of at least one monomer selected from the group consisting of 1,1-difluoroethylene, and may be used by blending the single or copolymer with a styrene-based resin, an epoxy resin, a polyester resin, or a polyurethane resin. It may be.

According to a preferred test example of the present invention, by varying the average particle diameter and content of the organic powder and measuring the image concentration, transfer efficiency, long-term and drum contamination, compared with the case of out of the average particle diameter and content suggested in the present invention It was found to be excellent in all the above tests (see Table 7).

Meanwhile, silica and titanium dioxide are used as the coating inorganic powder to form the second coating layer 30 according to the present invention.

Of the inorganic powder present in the second coating layer 30, silica lowers the adhesion to the drum to improve the transfer efficiency of the toner, and due to the low electrical resistance of titanium dioxide, the silica has a charging characteristic corresponding to a specific range of the toner particle layer on the sleeve. Branches increase the number of toner particles relatively to increase the gradation. Specifically, the silica is coated on the surface of the titanium dioxide by mixing silica having a relatively small particle size and titanium dioxide having a relatively large particle size.

Although it is difficult to limit the thickness of the second coating layer 30 similarly to the first coating layer 20, the first coating layer 20 is formed to form a spherical shape with respect to the toner base particles 10. The second coating layer 30 formed on this layer may be formed to a relatively uniform thickness, it is formed to a thickness of 3 nm to 400 nm.

The silica is excellent in peelability and serves to lower the adhesion between the toner and the drum, and a particle size of 3-40 nm, preferably 5-30 nm, is used. At this time, when the particle size of the silica is larger than 40 nm, the adhesive strength with the first coating layer 20 is lowered. When the silica particle size is smaller than 3 nm, the adhesive force between the toner and the drum cannot be lowered sufficiently, so that the silica is properly selected within the above range.

The silica content is determined in consideration of the adhesion between the toner and the drum and the adhesion between the first coating layer 20, and preferably 1.0 to 4.0 parts by weight, preferably 100 parts by weight of the toner base particles 10, respectively. To 1.5 to 3.5 parts by weight. If the content exceeds 4.0 parts by weight, the adhesive strength with the first coating layer 20 is lowered, and due to the environmental dependence of silica, burn density stains occur under low temperature and low humidity environments, or contamination problems of non-image parts under high temperature and high humidity conditions are serious. When the amount is less than 1.0 part by weight, it is difficult to obtain a decrease in adhesion between the toner particles and the drum due to the addition of silica, resulting in a problem that the transfer efficiency is lowered.

The usable silica can be used by treating the silica surface with a surface treatment agent to improve environmental characteristics of maintaining the charging efficiency by maintaining the charging properties under the silica itself or high temperature, high humidity or low temperature and low humidity. At this time, the surface treatment may be used a silane compound, typically dimethyldichlorosilane (Dimethyldichlorosilane), dimethylpolysiloxane (Dimethylpolysiloxane), hexamethyldisilazane (Hexamethyldisilazane), aminosilane (Aminosilane), alkylsilane (Alkylsilane, octamethylcyclo It is used by modifying with a surface modifier selected from the group consisting of tetrasiloxane (Octamethylcyclotetrasiloxane).

Titanium dioxide has lower electrical resistance and higher charge exchangeability than silica, which narrows the charge distribution, improves gradation, makes images look smoother, reproduces photographic images, and compensates for the low environmental dependence of silica. . Preferably, the titanium dioxide may be used alone or in combination with a stable rutile at high temperature or anatase structure at low temperature, and may be used in a range of 80 to 200 nm, preferably 100 to 150 nm. Use within range. If the particle size of the titanium dioxide is larger than 200 nm, the adhesion with the first coating layer 20 is lowered, if smaller than 80 nm it is impossible to obtain the effect of the addition of titanium dioxide and select the one within the above range.

The content of such titanium dioxide is preferably used in an amount of 0.1 to 2.0 parts by weight, preferably 0.15 to 1.8 parts by weight, based on 100 parts by weight of the toner base particles, respectively. If the content exceeds 2.0 parts by weight, the adhesion with the first coating layer 20 becomes difficult and scratches may occur on the photosensitive drum, resulting in drum filiming, and if less than 1.0 part by weight, titanium dioxide is added. Since the effect by which it cannot be acquired is adjusted suitably within the said range.

According to a preferred test example of the present invention, by varying the average particle diameter and content of the silica and titanium dioxide, and measured the image concentration, transfer efficiency, long-term stability and drum contamination, the average particle diameter and content of the present invention It was found to be excellent in all the above tests compared to the case (see Table 8 and Table 11).

Hereinafter, the preparation of the nonmagnetic one-component color toner according to the present invention will be described in more detail at each step.

a) coating organic powder manufacturing step

In step a), two spherical organic powders are mixed to coat the particles with each other on the surface of each particle.

Preferably, the spherical organic powder is one of the organic powder is selected to have a small particle size, the other organic powder is selected to have a relatively large particle size to facilitate particle coating between each other.

Coating of organic powders according to the present invention is different from coating by a method such as deposition, and the concept of mixing for carrying out the coating is also distinguished from the meaning of simple mixing of general powders. That is, the mixing of the two organic powders of the present invention and the coating between the particles may be performed by blending organic powders having a specific functional group so that one oil-feeling powder is attached or buried at a specific position on the surface of another organic powder. The characteristics of the various kinds of organic powder can be displayed simultaneously.

At this time, the mixing is suitable for mechanical mixing using one type of mixer selected from the group consisting of Henschel mixer, turbine type stirrer, super mixer and hybridizer, and preferably 1 to 10 m / s, preferably 3 to 7 m / s. By stirring for 1 to 5 minutes at speed. These conditions can be appropriately changed by factors such as the type of mixer used and the processing capacity.

b) primary coating step

In step b), the coating organic powder obtained in a) is mixed with the toner base particles to coat the surface of the toner base particles to form a first coating layer.

The coating is typically made by injecting into a mixer as described above capable of a mechanical mixer followed by stirring for 5 to 20 minutes at a rate of 5 to 30 m / s, preferably 10 to 20 m / s. This mechanical mixing prevents the spherical coating organic powder from leaving the coated organic powder by facilitating the fixing of the toner base particle surface.

c) coating inorganic powder manufacturing step

In step c), two kinds of spherical inorganic powders, silica and titanium dioxide, are mixed in a constant ratio to coat the particles with each other on the surface of each particle.

In this case, the mixing is performed using the same or similar mixer as in step a), and is stirred for 1 minute to 5 minutes at a speed of 1 to 10 m / s, preferably 3 to 7 m / s, similarly to step a). Is done.

d) secondary coating step

In step d), the coating inorganic powder obtained in c) is mixed with the toner base particles having the first coating layer formed in step b) to second coat the surface of the toner base particles to form a second coating layer to form a nonmagnetic monocomponent toner. Prepare the particles.

The coating is typically made by injecting into a mixer as described above with a mechanical mixer capable of stirring for 5 to 20 minutes at a rate of 5 to 30 m / s, preferably 10 to 20 m / s, similarly to step b). .

The non-magnetic one-component color toner prepared through the steps described above has a particle size of 20 μm or less, preferably 3 to 15 μm, and has properties required as toner particles, that is, image density, transfer efficiency, and long-term improvement. The castle and drum pollution prevention ability is improved to show high conductivity, antistatic property and high color.

Specifically, the non-magnetic one-component color toner not only reduces the pressure between the sleeve and the charging blade, but also reduces the cohesion between the toner particles that increase as the pressure of the charging blade continues to increase, thereby reducing the coherence between the toner particles and the toner particles. Prevents particles from agglomerating with each other to maintain a uniformly charged state as always. In addition, it is possible to maintain high transfer efficiency, improve long-term stability, and reduce waste toner generation by showing uniform charging characteristics by injecting amorphous toner base particles into concave portions by spherical organic powders. This can be called.

Non-magnetic one-component color toners having such characteristics are preferably applied to indirect transfer or tandem high speed color printers, which are frequently used in accordance with recent trends in colorization and speed.

In the present invention, the average particle diameter means the number average particle diameter unless otherwise specified.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only examples of the present invention, and the present invention is not limited to these examples.

Example  One

1-1: Cyan Toner Parent  Produce

94 parts by weight of polyester resin (number average molecular weight: 2.5 × 105), 5 parts by weight of phthalocyanine P.BI.15: 3, 1 part by weight of metal azo salt and 3 parts by weight of low molecular weight polypropylene as a charge control agent It was. This was melt kneaded at a temperature of 165 DEG C in biaxial melt kneading, pulverized by a jet mill grinder, and classified in a wind classifier to prepare toner base particles having a volume average particle diameter of 7.2 mu m.

1-2: Preparation of the first coating layer

0.5 parts by weight of polytetrafluoroethylene having an average particle diameter of 0.1 µm and 0.5 parts by weight of PMMA having a diameter of 0.1 µm were injected into a Henschel mixer with respect to 100 parts by weight of the toner base particles prepared above, and then a tip speed of 5 m. Agitated at / s to coat each other to prepare a coated organic powder. The coated organic powder was first coated on the toner base particles by stirring the toner base particles prepared in Example for 5 minutes at a speed of 15 m / s using a Henschel mixer.

1-3: Preparation of Second Coating Layer

Subsequently, 2.5 parts by weight of silica (17 nm) and 1.0 part by weight of titanium dioxide (150 nm) were coated with each other at a rate of 5 m / s to prepare a coated inorganic powder. The coated inorganic powder was stirred and mixed at 15 m / s for 5 minutes using a Henschel mixer again to the toner base particles coated with the organic powder of the previous step to perform a secondary coating on the surface.

Example  2 to 25: nonmagnetic One-component color  Manufacture of toner

A nonmagnetic one-component color toner was prepared in the same manner as in Example 1, except that the composition as shown in Table 1 was used to determine the effect of particle size and content of the spherical organic powder. In this case, polytetrafluoroethylene (PTFE), polymethylmethacrylate (PMMA), polyvinylidene fluoride (PVDF) and silicon powder were used as the organic powder. The average particle diameter of 0.1 to 1.5㎛ was carried out while varying in the range of 0.5 to 1.5 parts by weight.

division Organic Powder Inorganic powder Silica Titanium dioxide Example 2 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 3 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 4 Average particle size 0.1㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 5 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 6 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 7 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 8 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 9 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 10 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 11 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 12 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 13 Average particle size 0.8㎛ PVDF 1.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 14 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 15 Average particle size 0.4㎛ 0.5 parts by weight of silicon powder Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 16 Average particle diameter 0.4㎛ 0.5 parts by weight of silicon powder Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 17 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 18 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.1㎛ PMMA 0.5 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 19 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.4㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 20 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.8㎛ PMMA 1.0 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 21 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Size 1.5㎛ PMMA 1.5 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 22 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 23 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 24 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.8㎛ PMMA 1.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 25 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 1.5㎛ PMMA 1.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight

Example  26 to 43: nonmagnetic One-component color  Manufacture of toner

A nonmagnetic one-component color toner was prepared in the same manner as in Example 1 except that the composition as shown in Table 2 was used to determine the effect of the particle size and content of the silica. At this time, the silica was performed while changing the average particle diameter of 6 to 40 nm in the range of 1.0 to 4.0 parts by weight.

division Organic powder Inorganic powder Silica Titanium dioxide Example 26 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 1.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 27 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 28 Average particle size 0.1㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 29 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 17nm 1.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 30 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 17nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 31 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 17nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 32 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 17nm 4.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 33 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 40nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 34 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 40nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 35 Average particle size 0.8㎛ PVDF 1.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 40nm 4.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 36 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle diameter 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 37 Average particle diameter 0.4㎛ 0.5 parts by weight of silicon powder Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 38 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 4.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 39 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.4㎛ PMMA 0.5 Parts by Weight Average particle size 17nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 40 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.8㎛ PMMA 1.0 Parts by Weight Average particle size 17nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 41 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Size 1.5㎛ PMMA 1.5 Weight Part Average particle size 17nm 4.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 42 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 30nm 1.0 parts by weight Average particle size 150nm 1.0 parts by weight Example 43 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.8㎛ PMMA 1.0 parts by weight Average particle size 30nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight

Examples 44-58 Preparation of Nonmagnetic One-Component Color Toner

A nonmagnetic one-component color toner was prepared in the same manner as in Example 1, except that the composition shown in Table 3 below was used to determine the effect of the particle size and content of titanium dioxide. At this time, the titanium dioxide was carried out while changing the average particle diameter of 80 to 200 nm in the range of 0.5 to 2.0 parts by weight.

division Organic Powder Inorganic powder Silica Titanium dioxide Example 44 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 1.0 parts by weight Average particle size 80nm 0.5 parts by weight Example 45 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 80nm 1.0 parts by weight Example 46 Average particle size 0.1㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 80nm 2.0 parts by weight Example 47 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight 0.5nm by weight of average particle diameter Example 48 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 49 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 2.0 parts by weight Example 50 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight 0.5nm by weight of average particle size 200nm Example 51 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 1.0 parts by weight Example 52 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 2.0 parts by weight Example 53 Average particle size 0.4㎛ 0.5 parts by weight of silicon powder Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 80nm 0.5 parts by weight Example 54 Average particle diameter 0.4㎛ 0.5 parts by weight of silicon powder Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 80nm 2.0 parts by weight Example 55 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight 0.5nm by weight of average particle diameter Example 56 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.1㎛ PMMA 0.5 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Example 57 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.4㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 2.0 parts by weight Example 58 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 2.0 parts by weight

Comparative example  1 to 25: nonmagnetic One-component color  Manufacture of toner

A nonmagnetic one-component color toner was prepared in the same manner as in Example 1 except that the particle size and content of the organic powder were changed as shown in Table 4 to compare with Examples 1 to 25. At this time, the organic powder was carried out while varying the content of the average particle diameter of 0.05 and 2.0 ㎛ to at least 0.05 parts by weight and up to 3.5 parts by weight.

division Organic Powder Inorganic powder Silica Titanium dioxide Comparative Example 1 Average particle size 0.05㎛ PTFE 0.05 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 2 Average particle size 0.05㎛ PTFE 0.05 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 3 Average particle size 0.05㎛ PTFE 0.05 weight part Average particle size 1.5㎛ PMMA 0.5 weight part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 4 Average particle diameter 2.0㎛ PVDF 2.5 parts by weight Average particle diameter 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 5 Average particle size 2.0㎛ PVDF 2.5 parts by weight Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 6 Average particle size 2.0㎛ PVDF 2.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 7 Average particle size 0.1㎛ PVDF 2.5 parts by weight Average particle size 0.05㎛ PMMA 0.05 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 8 Average particle size 0.1㎛ PVDF 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 9 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 10 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 11 Average particle size 1.5㎛ PVDF 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 12 Average particle size 0.05㎛ PVDF 0.05 weight part Average particle size 2.0㎛ PMMA 3.0 weight part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 13 Average Particles 0.05㎛ Silicon Powder 0.05 Parts by Weight Average Particles 0.1㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 14 Average Particles 0.05㎛ Silicon Powder 0.05 Parts by Weight Average Particles 0.4㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 15 Average Particles 0.05㎛ Silicon Powder 0.05 Parts by Weight Average Particles 0.8㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 16 Average Particles 0.05㎛ Silicon Powder 0.05 Parts by Weight Average Particles 1.5㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 17 Average Particles 0.05㎛ Silicon Powder 0.05 Parts by Weight Average Particles 2.0㎛ PMMA 3.0 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 18 Average Particle Size 0.1㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.05㎛ PMMA 0.05 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 19 Average Particles 0.4㎛ Silicon Powder 1.0 parts by weight Average Particles 0.05㎛ PMMA 0.05 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 20 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.05㎛ PMMA 0.05 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 21 Average particle size 1.5㎛ Silicon powder 1.5 parts by weight Average particle size 0.05㎛ PMMA 0.05 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 22 Average particle size 0.4㎛ Silicon powder 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 23 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 2.0㎛ PMMA 3.5 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 24 Average particle size 1.5㎛ Silicon powder 1.0 parts by weight Average particle size 2.0㎛ PMMA 3.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 25 Average Particle Size 2.0㎛ Silicon Powder 2.5 Parts by Weight Average Particle Size 2.0㎛ PMMA 3.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight

Comparative example  26 to 42: nonmagnetic One-component color  Manufacture of toner

Non-magnetic one-component color toner was prepared in the same manner as in Example 1 while varying the particle size and content of the silica powder as shown in Table 5 to be compared with Examples 26 to 43. In this case, the silica was used having an average particle diameter of 2 to 50 nm, and the content was carried out while varying the content to at least 0.5 parts by weight and at most 5.0 parts by weight.

division Organic Powder Inorganic powder Silica Titanium dioxide Comparative Example 26 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 2nm 1.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 27 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 2nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 28 Average particle size 0.1㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 2nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 29 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 2nm 0.3 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 30 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 2nm 0.5 Average particle size 150nm 1.0 parts by weight Comparative Example 31 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 2nm 5.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 32 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 50nm 1.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 33 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 50nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 34 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 50nm 3.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 35 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 50nm 4.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 36 Average particle size 1.5㎛ PVDF 1.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 50nm 5.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 37 Average particle size 0.8㎛ PVDF 1.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight 0.5 nm by weight of average particle size 17nm Average particle size 150nm 1.0 parts by weight Comparative Example 38 Average particle size 0.4㎛ 0.5 parts by weight of silicon powder Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 17nm 5.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 39 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle diameter 0.4㎛ PMMA 0.5 parts by weight Average particle size 26nm 0.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 40 Average particle diameter 0.4㎛ 0.5 parts by weight of silicon powder Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 26nm 5.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 41 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle size 1.5㎛ PMMA 0.5 parts by weight 0.5nm by weight of average particle size 40nm Average particle size 150nm 1.0 parts by weight Comparative Example 42 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.1㎛ PMMA 0.5 Weight Part Average particle size 40nm 5.0 parts by weight Average particle size 150nm 1.0 parts by weight

Comparative example  43 to 58: nonmagnetic One-component color  Manufacture of toner

A nonmagnetic one-component color toner was prepared in the same manner as in Example 1 except that the particle diameters and contents of the titanium dioxide powder were changed as shown in Table 6 to be compared with Examples 44 to 61. At this time, the titanium dioxide was used having an average particle diameter of 50 to 300nm, the content was carried out while varying the content to at least 0.5 parts by weight and up to 5.0 parts by weight.

division Organic Powder Inorganic powder Silica Titanium dioxide Comparative Example 43 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 1.0 parts by weight Average particle size 50nm 0.05 parts by weight Comparative Example 44 Average particle size 0.1㎛ PTFE 0.5 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 50nm 2.5 parts by weight Comparative Example 45 Average particle size 0.1㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle diameter 150nm 0.05 parts by weight Comparative Example 46 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle diameter 150nm 2.5 parts by weight Comparative Example 47 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 0.05 parts by weight Comparative Example 48 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 2.5 parts by weight Comparative Example 49 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 200nm 0.05 parts by weight Comparative Example 50 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 250nm 1.0 parts by weight Comparative Example 51 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 250nm 2.0 parts by weight Comparative Example 52 Average particle size 0.4㎛ 0.5 parts by weight of silicon powder Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 250nm 2.5 parts by weight Comparative Example 53 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle diameter 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 250nm 0.05 parts by weight Comparative Example 54 Average particle diameter 0.4㎛ 0.5 parts by weight of silicon powder Average particle diameter 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 300nm 0.5 parts by weight Comparative Example 55 Average particle diameter 0.4㎛ 0.5 parts by weight Silicone powder Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 300nm 1.0 parts by weight Comparative Example 56 Average Particle Size 0.8㎛ Silicon Powder 1.0 Weight Part Average Particle Diameter 0.1㎛ PMMA 0.5 Weight Part Average particle size 6nm 2.5 parts by weight Average particle size 300nm 2.0 parts by weight Comparative Example 57 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.4㎛ PMMA 0.5 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 300nm 2.5 parts by weight Comparative Example 58 Average Particle Size 0.8㎛ Silicon Powder 1.0 Parts by Weight Average Particle Size 0.8㎛ PMMA 1.0 Parts by Weight Average particle size 6nm 2.5 parts by weight Average particle size 300nm 0.05 parts by weight

Comparative example  59 to 64: nonmagnetic One-component color  Manufacture of toner

A double coating layer and a single coating layer were formed on the surface of the toner base particles to examine the effect of the sequential formation of the first coating layer and the second coating layer as in the present invention.

Organic powder and inorganic powder having the same composition as in Examples 5 to 10 were prepared, organic powders were mixed to prepare mixed organic powders, inorganic powders were mixed to prepare organic and coated inorganic powders, and then toner was mixed in a Henschel mixer. A mother particle, a mixed organic powder and a mixed inorganic powder were injected and stirred at 15 m / s for 5 minutes to prepare a nonmagnetic one-component color toner.

division Organic Powder Inorganic powder Silica Titanium dioxide Comparative Example 59 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 60 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 61 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 62 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 63 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 64 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight

Comparative example  65 to 70: nonmagnetic One-component color  Manufacture of toner

A double coating layer and a multi coating layer were formed on the surface of the toner base particles to examine the effects of the sequential formation of the first coating layer and the second coating layer as in the present invention.

The organic powder and the inorganic powder having the same composition as in Examples 5 to 10 were prepared, and the toner base particles and one organic powder were injected into the Henschel mixer to perform one-step coating, followed by another one of the organic powders. To perform a two-stage coating, a three-stage coating using silica and a four-stage coating using titanium dioxide to prepare a non-magnetic one-component color toner. The stirring was carried out for 5 minutes at a speed of 15 m / s.

division Organic Powder Inorganic powder Stage 1 Tier 2 Stage 3 (Silica) 4th stage (titanium dioxide) Comparative Example 65 Average particle diameter 0.4㎛ 0.5 parts by weight PVDF Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 66 Average Particle Size 0.4㎛ PVDF 1.0 Weight Part Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 67 Average Particle Size 0.4㎛ PVDF 1.0 Weight Part Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 68 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 69 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 70 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight

Comparative example  71 to 84

When the double coating layer is formed on the surface of the toner base particles, the organic powder particles are coated first without coating the organic powder particles and the inorganic particles with each other, and then the inorganic particles are coated on the toner mother particles. It carried out to confirm the effect of the case.

In particular, Comparative Examples 71-84 prepared an organic powder and an inorganic powder having the same composition as in Examples 5 to 10, injecting the toner base particles and the organic powder into the Henschel mixer without precoating the organic particles and the inorganic particles. A step coating was performed, followed by a two step coating using silica and titanium dioxide to prepare a nonmagnetic one-component color toner. The stirring was carried out for 5 minutes at a speed of 15 m / s.

division Organic Powder Inorganic powder Silica Titanium dioxide Comparative Example 71 Average particle diameter 0.4㎛ 0.5 parts by weight PVDF Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 72 Average Particle Size 0.4㎛ PVDF 1.0 Weight Part X Average particle size 150nm 1.0 parts by weight Comparative Example 73 Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 74 Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 75 Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight X Comparative Example 76 Average particle size 0.4㎛ PMMA 0.5 parts by weight X Average particle size 150nm 1.0 parts by weight Comparative Example 77 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 78 Average particle size 0.8㎛ PVDF 1.0 parts by weight X Average particle size 150nm 1.0 parts by weight Comparative Example 79 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 6nm 2.5 parts by weight X Comparative Example 80 Average particle size 0.4㎛ PVDF 0.5 parts by weight Average particle size 1.5㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 81 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.0 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 82 Average particle size 0.4㎛ PVDF 1.0 parts by weight Average particle size 0.8㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 83 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.1㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight Comparative Example 84 Average particle size 0.8㎛ PVDF 1.0 parts by weight Average particle size 0.4㎛ PMMA 0.5 parts by weight Average particle size 6nm 2.5 parts by weight Average particle size 150nm 1.0 parts by weight

Test Example  One

In order to measure the physical properties of the non-magnetic one-component color toners prepared in Examples and Comparative Examples, a commercially available non-magnetic one-component development printer composed of a tandem developing mechanism using color toners (HP4600, Hewlett-Packard Co., Ltd.) to print up to 5,000 sheets at room temperature, humidity (20 ℃, 55% RH) conditions to the image density, transfer efficiency, long-term and charge roller (PCR) by the following method It measured based on.

1. Image density (ID) :

Solid area images were measured with a Macbeth reflection densitometer RD918 and the results obtained were divided into A, B, C and D grades, as follows.

A: Average density of images is 1.4 or more

B: The density of the image is 1.3 or more on average

C: Image density is 1.2 or less on average

D: Image density is 1.0 or less on average

2. Transfer efficiency (%) :

By printing up to 5000 sheets of paper, the net consumption was calculated by subtracting the waste from the consumption for each 500 sheets, and the percentage of toner transferred purely to paper was calculated. The results obtained at this time were divided into A, B, C and D grades, and the criteria are as follows.

A: Transfer efficiency 80% or more B: Transfer efficiency 70 to 80%

C: Transfer efficiency 60 to 70% D: Transfer efficiency 50 to 60%

3. Long term :

By printing up to 5000 sheets of paper, it was confirmed whether the image density and the transfer efficiency were maintained up to 5000 sheets. The results obtained at this time were divided into A, B, C and D grades.

A: Up to 5000 sheets of I.D. 1.4 or higher, 75% or higher transfer efficiency

B: Up to 5000 sheets I.D. 1.3 or more, 70% or more transfer efficiency

C: Up to 5000 sheets I.D. 1.2 or less, 60% or more transfer efficiency

D: Up to 5000 sheets I.D. 1.0 or less, 40% or more of transfer efficiency

4. Charge roller ( PCR ) contamination :

After printing up to 5000 sheets of paper and transferring the toner on the paper, the remaining toner on the PCR surface was adhered to a transparent tape, and the tape was attached to a white paper. Then, the result was visually measured using an optical microscope. Divided.

(Double-circle): Contamination of a charge roller generate | occur | produces severely.

(Circle): Slight contamination of the charge roller generate | occur | produces.

(Triangle | delta): The contamination of a charge roller generate | occur | produces finely.

X: No contamination of the charging roller.

(1) Difference according to particle size and content of organic powder

Image density, transfer efficiency, long-term and contamination of the charging roller of the nonmagnetic one-component toner prepared in Examples 1 to 25 and Comparative Examples 1 to 25 to determine the difference in particle size and content of the organic powder based on the above criteria. Measurements were made and the results obtained are shown in Table 10 below.

division Burn density Transcription efficiency Long-term PCR contamination Example 1 A A B × Example 2 B A B × Example 3 A A A × Example 4 A A A × Example 5 A A A × Example 6 A A A × Example 7 A A A × Example 8 A A A × Example 9 A A A × Example 10 A A A × Example 11 A A A × Example 12 A A A × Example 13 A B A × Example 14 A A A × Example 15 A A A × Example 16 A A A × Example 17 A A A × Example 18 A A A × Example 19 B A A × Example 20 A A A × Example 21 A A A × Example 22 A A A × Example 23 A A A × Example 24 A A A × Example 25 A A B × Comparative Example 1 D D D ○ Comparative Example 2 D D C ○ Comparative Example 3 C D D ○ Comparative Example 4 D D D ◎ Comparative Example 5 D D C ◎ Comparative Example 6 C D D ◎ Comparative Example 7 C D D ◎ Comparative Example 8 D D D ◎ Comparative Example 9 C D D ◎ Comparative Example 10 C D D ◎ Comparative Example 11 D D D ◎ Comparative Example 12 D D D ◎ Comparative Example 13 D D D ○ Comparative Example 14 D C D ○ Comparative Example 15 D D D ○ Comparative Example 16 D D D ○ Comparative Example 17 C D D ◎ Comparative Example 18 D D D ○ Comparative Example 19 D D D ○ Comparative Example 20 D D D ○ Comparative Example 21 D D D ○ Comparative Example 22 D D D ◎ Comparative Example 23 D D D ◎ Comparative Example 24 D D D ◎ Comparative Example 25 D D D ◎

Referring to Table 11, after the spherical organic powders were coated and adhered to each other according to the present invention, silica and titanium dioxide were coated to each other to adhere to each other, and then the multi-step coating was performed to coat these particles on the surface of the toner base particles. Color toners of Examples 1 to 25 were found to be excellent in image density, transfer efficiency, and long-term compared to Comparative Examples 1 to 25. This has the effect of spherical organic powder being first coated on the surface of the toner base particles to make it spherical, thereby making silica and titanium dioxide particles adhere well to the toner base particles, as well as the cohesion force between the toner particles. It can be seen that it helps to maintain the charging characteristics by reducing the role of).

(2) Difference according to particle size and content of silica powder

In order to determine the difference in particle size and content of the silica powder based on the above criteria, the image concentration, transfer efficiency, long-term and PCR contamination of the nonmagnetic one-component toner prepared in Examples 26 to 42 and Comparative Examples 26 to 42 were measured. The results obtained are shown in Table 11 below.

division Burn density Transcription efficiency Long-term PCR contamination Example 26 A A A × Example 27 A A A × Example 28 A A A × Example 29 A A A × Example 30 A A A × Example 31 A A A × Example 32 A A A × Example 33 A A A × Example 34 A A A × Example 35 A A A × Example 36 A A A × Example 37 A A A × Example 38 B A A × Example 39 A A B × Example 40 A A A × Example 41 A A A × Example 42 A A A × Comparative Example 26 D D D ○ Comparative Example 27 D D D ○ Comparative Example 28 D D D ○ Comparative Example 29 D D D ◎ Comparative Example 30 D D D ○ Comparative Example 31 D D D ◎ Comparative Example 32 D D D ◎ Comparative Example 33 D D D ◎ Comparative Example 34 D D D ○ Comparative Example 35 D D D ○ Comparative Example 36 D D D ○ Comparative Example 37 D D D ◎ Comparative Example 38 D D D ◎ Comparative Example 39 D C D ◎ Comparative Example 40 D D D ○ Comparative Example 41 D D D ◎ Comparative Example 42 D D D ○

Referring to Table 11, the color toners of Examples 28 to 50 containing 1 to 4 parts by weight of silica having an average particle diameter of 3 to 40 nm according to the present invention are compared with the color toner of Comparative Examples 26 to 42. The results were excellent in all the properties of, transfer efficiency, long term and PCR contamination prevention.

(3) Difference according to particle size and content of titanium dioxide powder

Image density, transfer efficiency, long term and PCR contamination of nonmagnetic one-component toners prepared in Examples 43 to 58 and Comparative Examples 43 to 58 to determine the difference in particle size and content of titanium dioxide powder based on the above criteria. And the results obtained are shown in Table 12 below.

division Burn density Transcription efficiency Long-term PCR contamination Example 43 A A A × Example 44 A B A × Example 45 A A A × Example 46 A A A × Example 47 A A A × Example 48 A A A × Example 49 A A A × Example 50 A A A × Example 51 A A A × Example 52 A A A × Example 53 A A A × Example 54 A A A × Example 55 A A A × Example 56 B A A × Example 57 A A A × Example 58 A A A × Comparative Example 43 D D D ◎ Comparative Example 44 C D D ○ Comparative Example 45 D D D ◎ Comparative Example 46 D D D ○ Comparative Example 47 D D C ◎ Comparative Example 48 D D D ○ Comparative Example 49 D D D ◎ Comparative Example 50 D D D ○ Comparative Example 51 D D D ○ Comparative Example 52 D D D ○ Comparative Example 53 D C D ◎ Comparative Example 54 D D D ◎ Comparative Example 55 D D D ○ Comparative Example 56 D D D ○ Comparative Example 57 D D D ○ Comparative Example 58 D D D ○

Referring to Table 12, the color toners of Examples 43 to 58 containing 0.1 to 2.0 parts by weight of titanium dioxide having an average particle diameter of 80 to 200 nm according to the present invention are compared with the color toner of Comparative Examples 43 to 58. Excellent results were obtained for all properties of concentration, transcription efficiency, long-term and PCR contamination prevention.

(4) the difference between the formation of a double coating layer in multiple steps and the formation of a single coating layer in one step

On the basis of the above criteria, in order to find out the difference between the case where the double coating layer was sequentially formed on the toner base particles in two stages as in the present invention, and when the single coating layer was formed using the same composition, Examples 5 to 10 above. And, the image concentration, transfer efficiency, long-term and PCR contamination of the non-magnetic one-component toner prepared in Comparative Examples 59 to 64 were measured, and the results obtained are shown in Table 13 below.

division Burn density Transcription efficiency Long-term PCR contamination Example 5 A A A × Example 6 A B A × Example 7 A A A × Example 8 A A A × Example 9 A A A × Example 10 A A A × Comparative Example 59 C D D ◎ Comparative Example 60 C D D ○ Comparative Example 61 B D D ◎ Comparative Example 62 C D D ○ Comparative Example 63 C D D ◎ Comparative Example 64 B D D ◎

Referring to Table 13, it can be seen that the toner particles of the example in which the double coating layer is formed are superior to the toner particles of the comparative example in which the single coating layer is formed.

Specifically, although the toner particles prepared in Comparative Examples 59 to 64 used organic powder and inorganic powder having the same composition and size as those of Examples 5 to 10, image density, transfer efficiency and long-term properties were very poor, and PCR It can be seen that the contamination is very serious. These results indicate that the organic powder and the inorganic powder coated on the surface of the toner base particles do not properly exhibit the characteristics unique to each powder by a single coating.

(5) Differences due to the formation of double coating layers and the formation of multiple coating layers

On the basis of the above criteria, in order to find out the difference between the case where the double coating layer was sequentially formed on the toner base particles in two steps as in the present invention, and when the multiple coating layer was formed using the same composition, Examples 5 to 10 above. And, the image concentration, transfer efficiency, long-term and PCR contamination of the non-magnetic one-component toner prepared in Comparative Examples 65 to 70 were measured, and the results obtained are shown in Table 14 below.

division Burn density Transcription efficiency Long-term PCR contamination Comparative Example 65 D C C ○ Comparative Example 66 C D D ○ Comparative Example 67 B D D ○ Comparative Example 68 C D D ○ Comparative Example 69 C D D ◎ Comparative Example 70 B D D ◎

Referring to Table 14, it can be seen that the toner particles of the example in which the double coating layer is formed are superior to the toner particles of the comparative example in which the multiple coating layer is formed.

Specifically, although the toner particles prepared in Comparative Examples 65 to 70 used organic powder and inorganic powder having the same composition and size as those of Examples 5 to 10, image density, transfer efficiency and long-term properties were very poor, and PCR It can be seen that the contamination is very serious. As a result of this, as in the result of Table 14, the organic powder and the inorganic powder coated on the surface of the toner base particles as in the present invention are the best when the double coating layer is formed in two steps after coating the respective powders. It means that it can have toner properties.

(6) Difference due to no coating process between organic particles or inorganic particles

division Burn density Transcription efficiency Long-term PCR contamination Comparative Example 71 D C C ○ Comparative Example 72 C D D ○ Comparative Example 73 D D D ○ Comparative Example 74 C D D ○ Comparative Example 75 D D D ◎ Comparative Example 76 C D D ◎ Comparative Example 77 D C D ◎ Comparative Example 78 C D D ◎ Comparative Example 79 D D C ◎ Comparative Example 80 D D D ◎ Comparative Example 81 D C C ○ Comparative Example 82 C D D ○ Comparative Example 83 D D D ○ Comparative Example 84 D D C ○

Referring to Table 15, it can be seen that the first coating of the organic particles and the coating of the inorganic particles exhibits much superior properties than otherwise. In particular, Comparative Examples 71 to 84 were composed of particles having the same composition and size as in Examples 5 to 10, but very poor in image density, transfer efficiency and long-term, and contamination of PCR was very serious. As a result of this, as in the result of Table 15, when the organic particles and the inorganic particles are first coated as in the present invention, it means that they may have the best toner properties.

Test Example  2

In order to determine the surface state of the first coating layer and the second coating layer formed according to the present invention, the particles obtained by coating two different types of organic powders on the toner base particles in Example 1 are coated on the toner base particles. Using the scanning electron microscope, the surface of the particles obtained by first coating and then the inorganic powder obtained by coating different inorganic powder particles with each other is coated with the first organic powder toner obtained above and then secondarily coated again. Was observed.

Figure 2 is a scanning electron microscope (SEM) photograph showing the surface state of the particles obtained after the primary coating on the toner base particles according to the present invention, Figure 4 is the surface of the particles obtained by secondary coating after the primary coating in accordance with the present invention Scanning electron micrograph showing the condition.

Referring to FIG. 2, it can be seen that the surface of the toner base particles is very irregular, and that the organic powder fills the concave portions of the toner base particles. In this case, as shown in FIG. 3, it can be seen that the two organic powders are actually coated with each other at the same time.

Referring to FIG. 4, it can be seen that the surface state of the toner particles is relatively uniform due to the first coating layer, and the mixed inorganic powder is uniformly formed on the surface of the toner particles. In this case, the inorganic powders are coated with each other in the form as shown in FIG. 5.

As described above, according to the present invention, a first coating layer comprising a coating organic powder mixed with two organic powders and coated on the surface of each other, and a coating inorganic powder coated with particles of silica and titanium dioxide A nonmagnetic one-component color toner including a second coating layer was prepared.

The color toner has a narrow charge distribution and high conductivity, which is excellent in image density and transfer efficiency, and improves long-term reliability and prevents contamination of photosensitive drums or charging rollers. It is preferably applied to a high speed color printer of an indirect transfer method or a tandem method used.

Claims (17)

A first coating layer and a second coating layer formed on the surface of the toner base particles, wherein the first coating layer contains a coating organic powder of two organic powders coated on each other surface, the second coating layer is silica and titanium dioxide Containing coated inorganic powder coated on the surface of each other, The organic powder is at least one monomer selected from the group consisting of styrene compounds, vinyl halides, vinyl esters, methacrylates, acrylic acid derivatives, acrylates, tetrafluoroethylene, and 1,1-difluoroethylene. Homopolymerized copolymers or copolymers; or The homopolymer or copolymer; A color toner for a nonmagnetic one-component printing system, which is a mixture of one or more resins selected from the group consisting of styrene resin, epoxy resin polyester resin, and polyurethane resin. The color toner of claim 1, wherein the first coating layer has a thickness of 10 nm to 200 nm. The method of claim 1, wherein the first coating layer comprises 0.1 to 2.0 parts by weight of each of the two organic powders with respect to 100 parts by weight of the toner base particles, The organic powder is at least one monomer selected from the group consisting of styrene compounds, vinyl halides, vinyl esters, methacrylates, acrylic acid derivatives, acrylates, tetrafluoroethylene, and 1,1-difluoroethylene. Homopolymerized copolymers or copolymers; or The homopolymer or copolymer; A color toner, characterized in that a mixture of one or more resins selected from the group consisting of styrene resins, epoxy resins, polyester resins, and polyurethane resins. The method of claim 1, wherein the organic powder has an average particle diameter of 0.1 ㎛ to 1.8 ㎛, the organic powder is a styrene compound, vinyl halides, vinyl esters, methacrylates, acrylic acid derivatives, acrylates, tetra Homopolymers or copolymers in which at least one monomer selected from the group consisting of fluoroethylene and 1,1-difluoroethylene is polymerized; or The homopolymer or copolymer; Color toner, characterized in that the mixture of at least one resin selected from the group consisting of styrene resin, epoxy resin polyester resin and polyurethane resin. delete The method of claim 1, wherein the styrene compound is selected from the group consisting of styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene and nonyl styrene, The vinyl halides are selected from the group consisting of vinyl chloride and vinyl fluoride, The vinyl esters are selected from the group consisting of vinyl acetate and vinyl benzoate, The methacrylates are selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and phenyl acrylate. Become, The acrylic acid derivatives are selected from the group consisting of acrylonitrile and methacrylonitrile, The acrylate is a color toner is selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate and phenyl acrylate. The nonmagnetic one-component color toner of claim 1, wherein the second coating layer has a thickness of 3 nm to 400 nm. The color toner of claim 1, wherein the second coating layer comprises 1.0 to 4.0 parts by weight of silica and 0.1 to 2.0 parts by weight of titanium dioxide based on 100 parts by weight of the toner base particles. The color toner of claim 1, wherein the silica has an average particle diameter of 3 nm to 40 nm. The method of claim 1, wherein the silica is silica itself; Or dimethyldichlorosilane, dimethylpolysiloxane, dimethylpolysiloxane, hexamethyldisilazane, hexamethyldisilazane, aminosilane, alkylsilane, and octamethylcyclotetrasiloxane. Color toner surface-treated with a surface modifier of; 2. The nonmagnetic one-component color toner of claim 1, wherein the titanium dioxide has an average particle diameter of 80 nm to 200 nm. The color toner of claim 1, wherein the titanium dioxide is selected from the group consisting of rutile, anatase type, and mixtures thereof. 2. The color toner of claim 1, wherein the toner base particles include a binder resin, a colorant, and a charge control agent. 14. The color toner of claim 13, wherein the toner base particles further comprise at least one selected from the group consisting of a flow promoter and a release agent.  a) mixing two spherical organic powders and coating them on the surface of each other to prepare a coated organic powder; b) coating the coated organic powder on the surface of the toner base particles to prepare toner base particles having a first coating layer; c) mixing silica and titanium dioxide and coating the surface of each other to prepare a coated inorganic powder; And d) coating the coated inorganic powder with toner base particles on the first coating layer of step b) to form a second coating layer; Including, The organic powder is at least one monomer selected from the group consisting of styrene compounds, vinyl halides, vinyl esters, methacrylates, acrylic acid derivatives, acrylates, tetrafluoroethylene, and 1,1-difluoroethylene. Homopolymerized copolymers or copolymers; or The homopolymer or copolymer; A method for producing a nonmagnetic one-component color toner, which is a mixture of one or more resins selected from the group consisting of styrene resin, epoxy resin polyester resin, and polyurethane resin. 16. The nonmagnetic one-component color toner according to claim 15, wherein Iii) 0.1 to 2.0 parts by weight of each of the two spherical organic powders having an average particle diameter of 0.1 탆 to 1.8 탆, Ii) 1.0 to 4.0 parts by weight of silica powder having an average particle diameter of 3 nm to 40 nm, Iii) 0.1 to 2.0 parts by weight of titanium dioxide powder having an average particle diameter of 80 nm to 200 nm, The organic powder is at least one monomer selected from the group consisting of styrene compounds, vinyl halides, vinyl esters, methacrylates, acrylic acid derivatives, acrylates, tetrafluoroethylene, and 1,1-difluoroethylene. Homopolymerized copolymers or copolymers; or The homopolymer or copolymer; A method for producing a color toner, characterized in that the mixture is at least one resin selected from the group consisting of styrene resin, epoxy resin polyester resin and polyurethane resin. 16. The method of claim 15, wherein the mixing of the steps a) to d) uses one mixer selected from the group consisting of a Henschel mixer, a turbine type stirrer, a super mixer, and a hybridizer. .

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