KR20060092363A - Color toner for non-magnetic mono-component system having excellent gradation and a method for preparing the same - Google Patents

Abstract

 The present invention relates to a non-magnetic one-component color toner having excellent gradation and a method of manufacturing the same. More specifically, toner base particles include organic powders of large and small diameters having different particle sizes, silica powder and titanium dioxide powder. The present invention relates to a nonmagnetic one-component color toner which is added and mechanically mixed at the same time and fixed on the surface of the toner base particles, and a manufacturing method thereof.

 The toner particles produced by the above method have a narrow charge distribution, exhibit high chargeability, improve charge retention, and in particular, have excellent gradation to realize high quality images.

 Non-magnetic one-component color toner, organic powder, silica, high chargeability, charge retention, high image density, high firing efficiency, long-term reliability, gradation

Description

 Non-magnetic one-component color toner having excellent gradation and manufacturing method thereof {COLOR TONER FOR NON-MAGNETIC MONO-COMPONENT SYSTEM HAVING EXCELLENT GRADATION AND A METHOD FOR PREPARING THE SAME}

 The present invention relates to a non-magnetic one-component color toner capable of improving image density, transfer efficiency, long-term and gradation, and a manufacturing method thereof.

Electrophotographic image formation generates static electricity to charge the surface of the photosensitive drum uniformly with a positive charge, and exposes the charged photosensitive drum surface to form an electrostatic latent image, and then is formed on the surface of the developing roller. Developing a latent image on the surface of the photosensitive drum using a toner having a negative charge to obtain a toner image, wherein the toner image is transferred and fixed on the transfer material, and then the toner remaining on the surface of the photosensitive drum is removed. It consists of.

In the toner developing step, good transfer performance is required for the toner charging amount, charge retention, environmental stability, and transfer process, low temperature fixability and offset resistance in the fixing process, and cleaning performance in the cleaning process. And various characteristics such as contamination resistance are required. Due to the recent rapid development of digital devices, high quality nitriding, high speed, and colorization are required to increase the complexity of the above characteristics.

In particular, higher and more accurate transfer performance and long-term stable charging performance are required for high quality, and it is necessary to reduce the amount of transfer residual toner, and in the case of full color, the image looks very coarse when the gradation of the actual printed image is low. It is not natural and greatly degrades the quality.

Generally, toners are classified into two-component toners in which a nonmagnetic one-component toner consisting of non-magnetic toner particles such as a binder resin, a colorant, and a charge control agent is mixed in a suitable mixing ratio of magnetic carrier particles and magnetic toner particles made of a synthetic resin.

Among them, nonmagnetic one-component toner controls the adhesion thickness of the toner layer formed on the developing roller and presses a blade made of metal or resin to pressurize the developing roller to charge the toner. When it is used repeatedly for a long time because of the pressure applied, the toner is easy to block on the developing roller and the blade, and the toner layer thickness and charge amount on the developing roller are uneven due to such fusion, resulting in uneven image density and There is a problem in that fog phenomenon and concentration unevenness occurs. The characteristics of such toner are influenced by the additives present on the surface, and at this time, the charging performance is controlled by blending the additives and changing 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 triboelectric 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 and 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, high chargeability, not only excellent image density and transfer efficiency, but also long-term stability and gradation to improve a non-magnetic one-component system An object of the present invention is to provide a color toner and a manufacturing method thereof.

In order to achieve the above object, the present invention provides a

I) large-diameter organic powder having a particle size of 0.3 µm to 2.0 µm;

Ii) small-diameter organic powder having a particle size of 0.05 µm to 0.25 µm;

V) silica powder having a particle size of 0.005 µm to 0.05 µm; And

I) A nonmagnetic one-component color toner comprising a titanium dioxide powder having a particle size of 0.1 µm to 0.8 µm.

The present invention also provides toner base particles

I) large-diameter organic powder having a particle size of 0.3 µm to 2.0 µm;

Ii) small-diameter organic powder having a particle size of 0.05 µm to 0.25 µm;

V) silica powder having a particle size of 0.005 µm to 0.05 µm; And

I) A method for producing a non-magnetic one-component color toner in which titanium dioxide powder having a particle size of 0.1 to 0.8 mu m is added and mechanically mixed at the same time to be fixed on the surface of the toner base particles.

Preferably, the color toner particles are based on 100 parts by weight of the toner base particles, i) 0.1 to 2.0 parts by weight of a large diameter organic powder; Ii) 0.1 to 2.0 parts by weight of small-diameter organic powder; V) 1.0 to 3.0 parts by weight of silica; And iii) 1.0 to 3.0 parts by weight of titanium dioxide.

The toner base particles preferably include a binder resin, a colorant, and a charge control agent.

In this case, the mixing is preferably performed within a linear speed range of 10 to 30 m / sec using one mixer selected from the group consisting of Henschel mixer, turbine type stirrer, super mixer and 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 largely related to the charge performance and the charge retention property of the toner. Thus, in the present invention, two organic powders having different particle sizes on the surface of the toner base particles, silica and dioxide The inorganic powder of titanium is coated to improve the performance required as a toner.

The toner base particles are not particularly limited in the present invention, and the binder toner, colorant, and charge control agent are essential components and may be used in any one of kneading pulverization, suspension polymerization, emulsification polymerization, and emulsion aggregation. Purchase and use directly manufactured or commercially available. In this case, the toner base particles may further include other additives such as a fluidity accelerator or a release agent, as necessary. For example, the toner base particles 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.

Examples of the binder resin that can be used include styrene monomers such as styrene, chloro styrene and vinyl styrene; olefin monomers such as ethylene, propylene, butylene and isoprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and Methylene aliphatic carboxylic acid ester monomers such as methacrylic acid dodecyl; vinyl ether monomers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl and isopropenyl ketone Single or copolymerized polymers with at least one monomer selected from the group consisting of monomers are possible. Preferably, polystyrene, styrene acrylate acrylic copolymer, styrene methacrylate alkyl copolymer, styrene acrylonitrile copolymer, styrene butadiene copolymer, styrene maleic anhydride copolymer, polyethylene, polypropylene, and bisphenol A alkylene oxide additive Phosphorus polyoxypropylene (2,2), ethylene glycol, poly tetramethylene glycol, etc., a polyester resin produced by polycondensation reaction with maleic acid, phthalic acid, citraconic acid, etc. is used. It can be used by blending with urethane, epoxy resin or silicone resin.

Colorants are used to form visible images 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, anthrakin compounds, azo metal complexes or allyl amide compounds, and those obtained by direct synthesis or commercially available are used. 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.

Magenta colorants include condensed nitrogen compounds, anthrakin, quinacridone compounds, base dye lake compounds, naphthol compounds, benzoimidazole compounds, thioindigo compounds, or perylene compounds, and rose bengal, 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 cyan colorants, phthalocyanine compounds and derivatives thereof, anthrakin compounds, or base dye lake compounds 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.

When the charge control agent is ancillary, metal azo dyes, salicylic acid compounds, and the like may be used. In the case of positive charge, nigrosine dyes, quaternary ammonium salts, and the like may be used.

Additional fluidity promoters are SiO ₂ , TiO ₂ , MgO, Al ₂ O ₃ , ZnO, Fe ₂ O ₃ , CaO, BaSO ₄ , CeO ₂ , K ₂ O, Na ₂ O, ZrO ₂ , CaO · SiO ₂ , and K ₂ O.TiO ₂ , Al ₂ O ₃ · 2SiO ₂ , one or more selected from the group consisting of It is suitably used within the content range.

Release agents are also used to prevent the toner base particles from being offset, 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.

In particular, in the present invention, toner base particles having the composition described above are coated with two organic powders having different particle sizes and inorganic powders of silica and titanium dioxide in order to improve various characteristics as toners. Improve the required performance

The organic powder is in contact with the surface of the charging blade (charging blade) during charging of the drum surface to reduce the friction resistance to reduce the frictional resistance received by the toner between the sleeve and the charging blade to prevent solid deposition on the drum or roller, the inorganic The silica in the powder lowers the adhesion to the drum to improve the transfer efficiency of the toner, and the titanium dioxide has a low electrical resistance, thereby relatively increasing the number of toner particles having a charging characteristic corresponding to a specific range of the toner particle layer on the sleeve, thereby increasing the gray scale. Let's do it.

In other words, the nonmagnetic one-component developing method of the present invention, unlike the conventional two-component developing method or the magnetic one-component developing method, does not have a magnetic force to hold the toner particles on the surface of the sleeve so that the toner particles are scattered during the developing process. The surface of the toner particles should be more strongly charged to prevent the back and the like. Accordingly, when the excessive charging process is performed, the toner fusion phenomenon, in which the surface of the toner particles melts and aggregates due to the frictional force generated when the charging blades and the toner particles are rubbed, becomes impossible and cannot be applied as toner particles. In addition, the conventionally manufactured and commercially available toner base particles have a very irregular irregular shape rather than a spherical shape. When the irregular toner base particles are used as they are, the protrusions of the parent particles are excessively charged and conversely concave. The portion lacks charging, and thus has irregular charging characteristics throughout the toner particles.

Accordingly, in the present invention, the surface of the toner base particles is coated with the organic powder so that the toner particles have uniform charging characteristics, so that the organic powder fills the concave portions of the toner base particles so as to have a spherical particle shape. Use spherical organic powders of various kinds.

The organic powder according to the present invention uses a large diameter having a particle size of 0.3 µm to 2.0 µm and a small diameter of 0.05 µm to 0.25 µm.

The large-diameter organic powder prevents excessively charged phenomenon by reducing frictional heat during friction between the charging blade and the sleeve in the charging process, thereby increasing the charging uniformity of the entire toner particles and improving the charge retention in the long term. At this time, when the particle diameter of the large-diameter particles is larger than 2.0 µm, the gap between the charging blade and the charging blade becomes too wide, so that the charging is not performed well or the pressure is too high, so that fusion occurs in other parts of the toner base particles. On the other hand, if the particle size of the particle is less than 0.3 ㎛ the effect of reducing the friction with the charging blade is almost weak, so no effect can be seen.

In addition, in the case of the small-diameter particles, unlike the large-diameter particles, rather than reducing the frictional heat between the charging blade it contributes to the improvement of the high chargeability and uniformity of the toner particles. In other words, the small diameter particles themselves have high charging characteristics and at the same time have a larger surface area than large diameter particles, thereby contributing more to the charging characteristics. In addition, the small-diameter organic powder particles also play a role of reducing the load on the cleaning blade during OPC drum cleaning. Therefore, by using a combination of large- and small-diameter organic powder particles having such an advantage, each effect is maximized to improve the charge retention, not only to ensure long-term reliability, but also to bias applied during printing. Also in the gradation indicating the resolution of the image, an excellent effect can be obtained by simultaneous use with titanium dioxide, which has a low electrical resistance and high charge exchangeability, thereby narrowing the charge distribution.

The organic powder is used in an amount of 0.1 to 2.0 parts by weight based on 100 parts by weight of the toner base particles, respectively.

If the content of the organic powder of large diameter is less than 0.1 part by weight, it is difficult to expect the charging uniformity to be obtained by reducing the excessive friction by adding a large diameter, and when exceeding 2.0 parts by weight, the friction between the charging blade and the sleeve can be lowered. Although charging uniformity can be obtained, a phenomenon in which the toner is fused may be caused by being partially subjected to excessive pressure by the aggregation of excessively large diameter particles. In addition, large diameter particles, which are relatively poor in coating property, are more easily released from the toner base particles due to the excessive use of the large diameter organic powder particles, and contamination of the drum or the charging roller may cause a phenomenon such as deterioration of transfer efficiency, thereby ultimately securing charge retention. Makes it difficult

In addition, when the content of the organic powder of the small diameter is less than 0.1 parts by weight, the content thereof is too small, so it is difficult to expect the effect of securing high chargeability by the small diameter particles having high chargeability. On the contrary, if it exceeds 2.0 parts by weight, high chargeability can be secured. However, as the printing proceeds, excessively used small diameter organic powder is separated from the surface of the toner particles, resulting in charging part contamination or contamination of the transfer belt. Therefore, side effects such as lowering of image performance and lowering of transfer efficiency occur.

Organic powder that can be used in the present invention is usually a polymer used in this field, typically styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene, nonyl styrene, etc. Ryu; Vinyl halides selected from the group consisting of vinyl chloride and vinyl fluoride; Vinyl acetates and vinyl esters of 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 blended with the single or copolymer with a styrene-based resin, an epoxy resin, a polyester resin, or a polyurethane resin. Can also be used.

Silica is excellent in peelability and serves to lower the adhesion between the toner and the drum. The silica has a particle size of 0.005 μm to 0.05 μm (5 nm to 50 nm), preferably 0.007 to 0.04 μm (7 nm to 40 nm), I use that. At this time, when the particle size of the silica is larger than 0.05 μm, detachment occurs due to difficulty in adhesion with the toner base particles, and when it is lower than 0.005 μm, the adhesion force between the toner and the drum cannot be sufficiently lowered and used appropriately within the above range.

The content of such silica is determined in consideration of the adhesion force and the particle size of the toner and the drum, preferably 1.0 to 3.0 parts by weight based on 100 parts by weight of the toner base particles. If the content exceeds 3.0 parts by weight, it is difficult to adhere to the toner base particles, causing separation, and due to the environmental dependence of silica, burn density stains occur under low temperature and low humidity conditions, or contamination problems of non-image parts under high temperature and high humidity conditions are serious. On the contrary, if it 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, and the transfer efficiency is lowered.

The usable silica may be surface-treated in order to secure hydrophobicity to prevent a decrease in image density due to the silica itself or the effects of moisture or the like during long-term storage. The surface treatment may be a silane compound, typically dimethyldichlorosilane, dimethylpolysiloxane, hexamethyldisilazane, aminosilane, aminosilane, alkylsilane, and octamethyl It is used by modifying it with a surface modifier selected from the group consisting of octamethylcyclotetrasiloxane.

Titanium dioxide has lower electrical resistance and higher charge exchangeability than silica, which narrows the charge distribution, improves gradation, makes images look smooth and reproduces photographic images, and also 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 within a particle size range of 0.1 μm to 0.8 μm. If the particle diameter of the titanium dioxide is larger than 0.8 mu m, adhesion with the toner base particles may be difficult, and separation may occur. If the particle diameter is smaller than 0.1 mu m, the titanium dioxide cannot be obtained and the effect of adding titanium dioxide is not obtained.

The content of the titanium dioxide is preferably used in an amount of 0.3 to 2.0 parts by weight based on 100 parts by weight of the toner base particles, and if the content exceeds 2.0 parts by weight, scratches are formed on the photosensitive drum and drum filiming. If less than 0.3 parts by weight, the effect of the addition of titanium dioxide can not be obtained, it is preferable to adjust appropriately within the above range.

In order to prepare the toner using the composition as described above, first, the toner base particles containing the binder, the colorant, and the release agent are injected into a mixer such as a Henschel mixer, a turbine type stirrer, a super mixer, and a hybridizer so as to suit each application. do.

Into the mixer, a large diameter organic powder, a small diameter organic powder, silica and titanium dioxide are injected to the toner base particles in a predetermined weight ratio, and then mechanically mixed within a linear speed range of 10 to 30 m / sec. In order to attach the large- and small-diameter organic powder to the toner base particles including the binder component, it is very important to stir at an appropriate speed as high shear force is required. In particular, the conventional toner particles are produced by electrostatic attraction due to simple mixing, but the organic powder, silica and titanium dioxide are fixed to the surface of the toner base particles due to the mechanical mixing proposed in the present invention. do.

The nonmagnetic one-component color toner obtained by this method has a particle size of 1 m to 15 m, preferably 3 m to 12 m. The non-magnetic one-component color toner is uniformly formed on the surface of the toner base particles, which has a spherical effect and contributes to the improvement of transfer efficiency and long-term, as well as eliminating the over resistance generated locally by the use of titanium dioxide. It improves the blurring phenomenon and narrows the charge distribution to improve the gradation. The non-magnetic one-component color toner according to the present invention having such characteristics is preferably applied to indirect transfer or tandem high speed color printers, which are widely used according to recent trends of colorization and speed.

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.

Production Example  : Cyan Toner Parent  Produce

94 parts by weight of polyester resin (number average molecular weight: 2.5 × 10 ⁵ ), 5.0 parts by weight of phthalocyanine P.BI.15: 3 pigment, 1.0 part by weight of metal azo salt and 3.0 parts by weight of low molecular weight polypropylene as charge control agent Mixed. 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 8.0 mu m.

Example  1: nonmagnetic One-component color  Preparation of Toner Particles

In order to coat the surface of the toner base particles obtained in the above preparation example, 100 parts by weight of the toner base particles were injected into the Henschel mixer, and then 0.5 parts by weight of polyvinylidene fluoride powder having an average particle diameter of 0.1 μm and polymethylmethacrylate of 0.4 μm. 0.5 parts by weight of acrylate powder, 2.0 parts by weight of silica powder modified by octylsilane with a particle diameter of 6 nm, and 0.5 parts by weight of titanium dioxide having a particle size of 0.1 μm of rutile structure were added at a linear speed of 20 m / s. Stirring for minutes gave color toner particles.

Example  2 to 24: nonmagnetic One-component color  Preparation of Toner Particles

Color toner particles were prepared in the same manner as in Example 1, except that the compositions shown in Table 1 were used, and the amounts of each used were as shown in Table 2 below. At this time, the particle size of the silica is shown in nm unit for convenience. The polyvinylidene fluoride, polymethylmethacrylate, silica and titanium dioxide powders of Table 1 below have a negative charge.

Furtherance Organic powder Polyvinylidene fluoride with 0.1 μm particle diameter 0.1 μm PVDF Polyvinylidene Fluoride with 0.4 µm Particle Size 0.4 μm PVDF Polymethylmethacrylate with 0.4 µm Particle Size 0.4 μm PMMA Polymethylmethacrylate with 1.5 µm Particle Size 1.5 μm PMMA Silica Modified with octylsilane with 6 nm particle size 6 nm SiO ₂ Modified with dimethyldichlorosilane with 12 nm particle size 12 nm SiO ₂ Modified with hexamethyldisilazane with 50 nm particle size 50 nm SiO ₂ Modified with 100 nm particle diameter silicone oil 100 nm SiO ₂ Titanium dioxide 0.1 μm rutile structure 0.1 μm R-TiO ₂ 0.2 μm anatase structure 0.2 μm A-TiO ₂ 0.8 μm rutile structure 0.8 μm R-TiO ₂ 0.8 μm anatase structure 0.8 μm A-TiO ₂ 1.4 μm rutile structure 1.4 μm R-TiO ₂

(Contents / weight part) Small Diameter Organic Powder Large Diameter Organic Powder Silica Titanium dioxide Example 2 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 6nmSiO ₂ (2.0) 0.1 μm R-TiO ₂ (1.5) Example 3 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 12 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (0.5) Example 4 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 12 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (1.5) Example 5 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 6nmSiO ₂ (3.0) 0.8 μm R-TiO ₂ (2.0) Example 6 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6 nm SiO ₂ (2.0) 0.8 μm A-TiO ₂ (2.0) Example 7 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6nmSiO ₂ (2.0) 0.1 μm R-TiO ₂ (0.5) Example 8 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 12nmSiO ₂ (2.0) 0.1 μm R-TiO ₂ (1.0) Example 9 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 12nmSiO ₂ (2.0) 0.2 μm A-TiO ₂ (2.0) Example 10 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6 nm SiO ₂ (3.0) 0.8 μm R-TiO ₂ (0.5) Example 11 0.1㎛ PVDF (2.0) 1.5 μm PMMA (1.5) 12 nm SiO ₂ (2.0) 0.8 μm A-TiO ₂ (1.0) Example 12 0.1㎛ PVDF (2.0) 1.5 μm PMMA (1.5) 12 nm SiO ₂ (2.0) 0.1 μm R-TiO ₂ (0.5) Example 13 0.1㎛ PVDF (2.0) 1.5 μm PMMA (1.5) 50 nm SiO ₂ (2.0) 0.1 μm R-TiO ₂ (1.0) Example 14 0.1㎛ PVDF (2.0) 1.5 μm PMMA (1.5) 50 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (2.0) Example 15 0.4㎛ PVDF (0.5) 1.5 μm PMMA (0.5) 100 nm SiO ₂ (3.0) 0.8 μm R-TiO ₂ (0.5) Example 16 0.4㎛ PVDF (0.5) 1.5 μm PMMA (1.0) 100 nm SiO ₂ (3.0) 0.8 μm A-TiO ₂ (1.0) Example 17 0.4㎛ PVDF (0.5) 1.5 μm PMMA (2.0) 6 nm SiO ₂ (2.0) 0.1 μm R-TiO ₂ (2.0) Example 18 0.4 μm PVDF (1.0) 1.5 μm PMMA (1.0) 12 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (1.0) Example 19 0.4㎛ PVDF (2.0) 1.5 μm PMMA (2.0) 50 nm SiO ₂ (2.0) 0.8 μm A-TiO ₂ (2.0) Example 20 0.4 μm PMMA (0.1) 1.5 μm PMMA (0.5) 100 nm SiO ₂ (2.0) 0.8 μm R-TiO ₂ (0.5) Example 21 0.4 μm PMMA (0.5) 1.5 μm PMMA (1.0) 6 nm SiO ₂ (2.0) 0.1 μm R-TiO ₂ (1.0) Example 22 0.4 μm PMMA (0.5) 1.5 μm PMMA (1.0) 12 nm SiO ₂ (2.0) 0.1 μm R-TiO ₂ (2.0) Example 23 0.4 μm PMMA (1.0) 1.5 μm PMMA (1.5) 50 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (1.0) Example 24 0.4 μm PMMA (2.0) 1.5 μm PMMA (2.0) 100 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (2.0)

Comparative example  1 to 46: color  Preparation of Toner Particles

Color toner particles were prepared by the same method as Examples 1 to 24, and the specific composition thereof was as shown in Table 3, except that the size and content of organic powder, silica, and titanium dioxide were changed. .

 (Contents / weight part) Small Diameter Organic Powder Large Diameter Organic Powder Silica Titanium dioxide Comparative Example 1 0.1 μm PVDF (0.1) 0.1 μm PVDF (0.5) 6nmSiO ₂ (0.5) 0.1 μm R-TiO ₂ (2.5) Comparative Example 2 0.1 μm PVDF (2.5) 0.4 μm PVDF (1.5) 12nmSiO ₂ (3.0) 0.2 μm A-TiO ₂ (0.1) Comparative Example 3 0.1 μm PVDF (2.5) 0.4 μm PMMA (0.5) 50 nmSiO ₂ (4.0) 0.8 μm R-TiO ₂ (2.5) Comparative Example 4 0.1 μm PVDF (2.5) 1.5 μm PMMA (0.5) 100 nm SiO ₂ (4.0) 0.8 μm A-TiO ₂ (2.5) Comparative Example 5 0.4 μm PVDF (2.5) 0.1 μm PVDF (0.5) 6nmSiO ₂ (4.0) 0.1 μm R-TiO ₂ (0.1) Comparative Example 6 0.1 μm PVDF (0.5) 0.4 μm PVDF (2.5) 100 nm SiO ₂ (0.5) 1.4 μm R-TiO ₂ (0.1) Comparative Example 7 0.4 μm PVDF (2.5) 0.4 μm PVDF (1.5) 6nmSiO ₂ (0.5) 0.1 μm R-TiO ₂ (2.5) Comparative Example 8 0.4 μm PVDF (2.5) 0.4 μm PMMA (0.5) 12nmSiO ₂ (2.0) 0.2 μm A-TiO ₂ (0.1) Comparative Example 9 0.4 μm PVDF (2.5) 1.5 μm PMMA (1.5) 50 nmSiO ₂ (2.0) 0.2 μm A-TiO ₂ (0.1) Comparative Example 10 0.4 μm PMMA (2.5) 0.1 μm PVDF (0.5) 100 nm SiO ₂ (0.5) 0.8 μm R-TiO ₂ (2.5) Comparative Example 11 0.4 μm PMMA (2.5) 0.1 μm PVDF (0.5) 100 nm SiO ₂ (4.0) 1.4 μm R-TiO ₂ (1.0) Comparative Example 12 0.4 μm PMMA (2.5) 0.4 μm PVDF (1.0) 6nmSiO ₂ (4.0) 0.8 μm A-TiO ₂ (0.1) Comparative Example 13 0.4 μm PMMA (0.05) 0.4 μm PMMA (1.0) 12 nm SiO ₂ (4.0) 0.1 μm R-TiO ₂ (2.5) Comparative Example 14 0.4 μm PMMA (2.5) 1.5 μm PMMA (1.0) 50 nmSiO ₂ (4.0) 0.1 μm R-TiO ₂ (2.5) Comparative Example 15 0.1 μm PVDF (0.5) 0.4 μm PVDF (1.0) 100 nm SiO ₂ (0.5) 0.8 μm R-TiO ₂ (2.5) Comparative Example 16 0.1 μm PVDF (1.5) 0.4 μm PMMA (1.0) 100 nm SiO ₂ (4.0) 0.8 μm A-TiO ₂ (2.5) Comparative Example 17 0.1 μm PVDF (1.5) 0.4 μm PMMA (1.0) 50 nm SiO ₂ (5.0) 1.4 μm R-TiO ₂ (2.0) Comparative Example 18 0.1 μm PVDF (0.5) 1.5 μm PMMA (2.0) 6nmSiO ₂ (0.5) 0.1 μm R-TiO ₂ (0.1) Comparative Example 19 0.4 μm PVDF (0.5) 0.4 μm PMMA (1.0) 12nmSiO ₂ (3.0) 0.1 μm R-TiO ₂ (1.5) Comparative Example 20 0.4 μm PVDF (0.05) 1.5 μm PMMA (1.0) 50 nmSiO ₂ (4.0) 0.8 μm R-TiO ₂ (2.5) Comparative Example 21 0.4 μm PVDF (2.0) 0.4 μm PMMA (1.0) 50 nm SiO ₂ (0.5) 0.8 μm A-TiO ₂ (2.5) Comparative Example 22 0.4 μm PVDF (2.0) 0.4 μm PMMA (1.0) 100 nm SiO ₂ (4.0) 1.4 μm R-TiO ₂ (1.5) Comparative Example 23 0.4 μm PVDF (0.05) 1.5 μm PMMA (1.0) 6nmSiO ₂ (2.0) 0.1 μm R-TiO ₂ (1.5) Comparative Example 24 0.4 μm PVDF (2.0) 1.5 μm PMMA (1.0) 12 nm SiO ₂ (4.0) 0.1 μm R-TiO ₂ (0.1) Comparative Example 25 0.4 μm PVDF (0.05) 0.4 μm PMMA (1.0) 50 nm SiO ₂ (2.0) 0.2 μm A-TiO ₂ (0.5) Comparative Example 26 0.4 μm PMMA (2.0) 0.1 μm PVDF (1.0) 100 nm SiO ₂ (0.5) 0.2 μm A-TiO ₂ (2.5) Comparative Example 27 0.4 μm PMMA (2.0) 0.1 μm PVDF (1.0) 00nm SiO ₂ (3.0) 1.4 μm R-TiO ₂ (2.5) Comparative Example 28 0.4 μm PMMA (0.5) 0.4 μm PVDF (1.0) 6nmSiO ₂ (4.0) 0.8 μm R-TiO ₂ (0.5) Comparative Example 29 0.4 μm PMMA (0.5) 0.4 μm PVDF (1.0) 6nmSiO ₂ (0.5) 0.8 μm R-TiO ₂ (2.5) Comparative Example 30 0.4 μm PMMA (0.5) 1.5 μm PVDF (0.05) 12 nm SiO ₂ (4.0) 0.8 μm A-TiO ₂ (1.5)

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 (Contents / weight part) Small Diameter Organic Powder Large Diameter Organic Powder Silica Titanium dioxide Comparative Example 31 0.4 μm PMMA (0.5) 0.1 μm PVDF (2.0) 50 nm SiO ₂ (5.0) 0.8 μm A-TiO ₂ (0.1) Comparative Example 32 0.4 μm PMMA (0.5) 0.4 μm PVDF (0.05) 100 nm SiO ₂ (0.3) 0.1 μm R-TiO ₂ (2.5) Comparative Example 33 0.4 μm PMMA (0.5) 0.4 μm PMMA (2.0) 6nmSiO ₂ (4.0) 0.2 μm A-TiO ₂ (0.1) Comparative Example 34 0.4 μm PMMA (0.5) 0.4 μm PMMA (2.0) 6nmSiO ₂ (0.5) 1.4 μm R-TiO ₂ (1.5) Comparative Example 35 1.5 μm PMMA (0.5) 0.1 μm PVDF (0.05) 12 nm SiO ₂ (5.0) 0.8 μm R-TiO ₂ (2.5) Comparative Example 36 1.5 μm PMMA (0.5) 0.4 μm PVDF (2.0) 12nmSiO ₂ (0.5) 0.8 μm A-TiO ₂ (1.5) Comparative Example 37 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 6nmSiO ₂ (2.0) - Comparative Example 38 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 12 nm SiO ₂ (2.0) - Comparative Example 39 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 12 nm SiO ₂ (2.0) - Comparative Example 40 0.1㎛ PVDF (0.5) 0.4 μm PVDF (0.5) 6nmSiO ₂ (3.0) - Comparative Example 41 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6 nm SiO ₂ (2.0) - Comparative Example 42 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6nmSiO ₂ (2.0) - Comparative Example 43 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 12nmSiO ₂ (2.0) - Comparative Example 44 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 12nmSiO ₂ (2.0) - Comparative Example 45 0.1 μm PVDF (1.0) 0.4 μm PMMA (1.0) 6 nm SiO ₂ (3.0) - Comparative Example 46 0.1㎛ PVDF (2.0) 1.5 μm PMMA (1.5) 12 nm SiO ₂ (2.0) -

Test Example  Property measurement

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.) was printed up to 5,000 sheets at room temperature, humidity (20 ℃, 55% RH) and measured by the following method image density, transfer efficiency, long-term and gradation.

1. Image density (ID) : Solid area images were measured with Macbeth reflection densitometer RD918, and the results obtained were divided into A, B, C and D grades, and the criteria are 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 consumption from the consumption for each 500 sheets. The percentage of toner transferred 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: 80% or more transfer efficiency B: 70 ~ 80% transfer efficiency

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

3. Long-term : Printing up to 5000 sheets of paper, it was confirmed that the image density and transfer efficiency is maintained up to 5000 sheets, the results obtained are divided into A, B, C and D grades, the criteria are as follows.

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, Transfer efficiency 60% or more

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

4. Gradation : Printed up to 5000 sheets of paper and printed charts with different toner coverage (gradation) in 500 sheets to check the implementation of halftone (gradation). For example, a toner coverage chart of 17% was printed and a 35% coverage chart was printed to measure the image density at this time, and then blurring was measured. At this time, the numerical values obtained from the gray scale measurement were divided into A, B, C and D grades by the following criteria.

A: Image density 0.4 or less on a 17% coverage chart

    Less than 1.0 on a 35% chart, no blurring.

B: Image density 0.5 or less on a 17% coverage chart

    Less than 0.9 on a 35% chart with some blurring.

C: Image density 0.6 or less on a 17% coverage chart

    Less than 0.8 on 35% chart with blurring.

D: Image density 0.6 or less on a 17% coverage chart

    Less than 0.8 on 35% chart, severe blurring.

The image density, transfer efficiency, long term and gradation obtained based on the above criteria are shown in Table 4 below.

Image density (I.D) Transfer efficiency (%) Long-term Gradation Example 1 B A A A Example 2 B A A A Example 3 A A A B Example 4 A A A A Example 5 A A A A Example 6 A A A A Example 7 A A A A Example 8 B A A A Example 9 A A A A Example 10 A A A A Example 11 A A A A Example 12 B A A A Example 13 A A A A Example 14 A A A A Example 15 A B A A Example 16 A A A A Example 17 A A A A Example 18 A A A A Example 19 A A B A Example 20 A A A A

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Image density (I.D) Transfer efficiency (%) Long-term Gradation Example 21 A A A A Example 22 A A A A Example 23 A A B A Example 24 A A A A Comparative Example 1 D D D D Comparative Example 2 D C D D Comparative Example 3 D D D D Comparative Example 4 D D D D Comparative Example 5 D C D D Comparative Example 6 D D C D Comparative Example 7 D D D D Comparative Example 8 C D D D Comparative Example 9 D D D D Comparative Example 10 D D D D Comparative Example 11 D D D D Comparative Example 12 D D D D Comparative Example 13 D D D D Comparative Example 14 C D D D Comparative Example 15 D D D D Comparative Example 16 D D D D Comparative Example 17 D D D D Comparative Example 18 D D C D Comparative Example 19 D D D C Comparative Example 20 C D D D Comparative Example 21 D D D D Comparative Example 22 D D D D Comparative Example 23 D D D C Comparative Example 24 D D D D Comparative Example 25 D D D D Comparative Example 26 D D D D Comparative Example 27 D D D D Comparative Example 28 D D D D Comparative Example 29 D D D D Comparative Example 30 D C D C Comparative Example 31 D D D D Comparative Example 32 D D D D Comparative Example 33 D D D D Comparative Example 34 D D D D Comparative Example 35 D D D D Comparative Example 36 D D D C Comparative Example 37 B A A D Comparative Example 38 B A A D Comparative Example 39 A A A D Comparative Example 40 A A B D Comparative Example 41 A A A D Comparative Example 42 A A A D Comparative Example 43 A A A D Comparative Example 44 B A A D Comparative Example 44 A A A D Comparative Example 45 A A A D Comparative Example 46 B A A D

Referring to Table 4, as in the present invention, by using an organic powder having a different particle size and a mixture of silica and titanium dioxide, it showed excellent characteristics in both image density, transfer efficiency, long-term and gradation. In particular, it can be seen that excellent results can be obtained by using titanium dioxide together in gray scale characteristics.

In particular, the toner particles prepared in Comparative Examples 37 to 46 may have more than some charging characteristics as they exhibit relatively excellent image density, transfer efficiency, and long-term properties, but are gray scaled according to no use of titanium dioxide. This is very poor.

Such gradation is an important factor for expressing a photograph or a picture to be printed similarly to reality, and is recognized as an important factor in evaluating the quality of an actual image. The toner having a low gradation characteristic manufactured in Comparative Examples 37 to 46 is Images printed using particles not only look very rough but also give an unnatural feel, while toner particles using titanium dioxide, as in the present invention, produce a natural image due to the excellent gradation characteristics.

As described above, according to the present invention, the coating of the toner base particles with different large and small spherical organic powders and silica and titanium dioxide on the toner base particles results in a narrow charge distribution, high chargeability, and improved charge retention and gradation. It is possible to manufacture a nonmagnetic one-component color toner capable of realizing an image.

Claims (11)

Toner base particles I) large-diameter organic powder having a particle size of 0.3 µm to 2.0 µm; Ii) small-diameter organic powder having a particle size of 0.05 µm to 0.25 µm; V) silica powder having a particle size of 0.005 µm to 0.05 µm; And Vi) a non-magnetic one-component color toner comprising a titanium dioxide powder having a particle size of 0.1 µm to 0.8 µm. The method of claim 1, wherein the color toner is based on 100 parts by weight of the toner base particles, V) 0.1 to 2.0 parts by weight of large-diameter organic powder; Ii) 0.1 to 2.0 parts by weight of small-diameter organic powder; V) 1.0 to 3.0 parts by weight of silica; And Vi) a non-magnetic one-component color toner comprising 1.0 to 3.0 parts by weight of titanium dioxide. The method of claim 1, wherein the organic powder is styrene, such as styrene, methyl styrene, dimethyl styrene, ethyl styrene, phenyl styrene, chloro styrene, hexyl styrene, octyl styrene, nonyl styrene; Vinyl halides selected from the group consisting of vinyl chloride and vinyl fluoride; Vinyl acetates and vinyl esters of 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 one or more monomers selected from the group consisting of 1,1-difluoroethylene, and blended with the single or copolymer and styrene-based resin, epoxy resin polyester resin or polyurethane resin. Non-magnetic one-component color toner, characterized in that for use. The method of claim 1, wherein the silica is silica or dimethyldichlorosilane, dimethylpolysiloxane, dimethylpolysiloxane, hexamethyldisilazane, aminosilane, alkylsilane, and octamethylcyclotetra A nonmagnetic one-component color toner, characterized by using one selected from the group consisting of a surface modifier selected from the group consisting of siloxane (octamethylcyclotetrasiloxane). The non-magnetic one-component color toner according to claim 1, wherein the titanium dioxide is used alone or in combination with Rutile or Anatase type. The nonmagnetic one-component color toner of claim 1, wherein the toner base particles include a binder resin, a colorant, and a charge control agent. 7. The nonmagnetic one-component color toner of claim 6, wherein the toner base particles further comprise a fluidity accelerator or a release agent. Toner base particles I) large-diameter organic powder having a particle size of 0.3 µm to 2.0 µm; Ii) small-diameter organic powder having a particle size of 0.05 µm to 0.25 µm; V) silica powder having a particle size of 0.005 µm to 0.05 µm; And V) A method for producing a non-magnetic one-component color toner, wherein titanium dioxide powder having a particle size of 0.1 µm to 0.8 µm is added and mechanically mixed at the same time to be fixed on the surface of the toner base particles. The method of claim 8, wherein the color toner particles are based on 100 parts by weight of the toner base particles, V) 0.1 to 2.0 parts by weight of large-diameter organic powder; Ii) 0.1 to 2.0 parts by weight of small-diameter organic powder; V) 1.0 to 3.0 parts by weight of silica; And Vi) a method for producing a nonmagnetic one-component color toner comprising 1.0 to 3.0 parts by weight of titanium dioxide. The method of claim 8, wherein the mixing is performed by using a mixer of at least one selected from the group consisting of a Henschel mixer, a turbine type stirrer, a super mixer, and a hybridization group. 9. The method of manufacturing a nonmagnetic one-component color toner according to claim 8, wherein the mixing is performed in a range of 10 to 30 m / sec linear velocity.