JP2010160173A - Toner for developing electrostatic charge image, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for developing an electrostatic charge image having excellent light resistance, capable of forming a high-saturation color image having a bright color tone free from color muddiness, and to provide an image forming method. <P>SOLUTION: In the toner for developing an electrostatic charge image including toner particles including at least a binding resin and a coloring agent, the coloring agent constituting the toner particle includes C.I. acid red 52. In the image forming method using a full color toner kit including at least four kinds of toners, a magenta coloring agent includes the C.I. acid red 52. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image used for color image formation by an electrophotographic method and an image forming method.

  In recent years, according to electrophotographic image formation using an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”), in addition to the formation of monochrome images conventionally used mainly for document creation, etc., full color An image can be formed. The full-color image forming method using such a toner does not require a printing plate, and can produce only the required number of sheets on demand. Therefore, it is mainly used in the light printing field where there are many opportunities to produce a small amount of printed matter. It came to be utilized (for example, refer patent document 1).

  In particular, when creating a full-color print such as a catalog or an advertisement, the toner is required to have high color reproducibility for the purpose of forming an image in which a color faithful to the original is reproduced. . That is, when a full color image is formed, the target color tone is reproduced by the secondary color formed by superposing the yellow toner, the magenta toner and / or the cyan toner in principle. It is required that these color toners that are the basis for the realization have high color reproducibility. Therefore, various colorants have been studied for the purpose of improving the color reproducibility of each color toner.

  For example, quinacridone pigments can be used as magenta colorants for color toners. The toner using the quinacridone pigment is widely used because it has excellent light resistance and can form an image having a magenta hue. However, since this quinacridone pigment has low dispersibility, it tends to cause color turbidity when an image is formed by overlaying color toners, so that it cannot satisfy the image printing on a high chroma display. .

  In particular, in recent years, the opportunity to output computer graphics images created on a display has increased. The color gamut obtained by electrophotographic image formation using conventional colorants and the color gamut obtained by color printing using conventional printing inks are much narrower than the color gamut formed on the display. Therefore, there is a problem that the image on the display cannot be output faithfully on paper or the like.

  Thus, a quinacridone pigment is not used alone but a dye added to improve the saturation is disclosed (for example, see Patent Document 2). Further, a combination of a quinacridone pigment and a naphthol pigment (for example, see Patent Document 3), and a combination of a quinacridone pigment and an anthraquinone pigment are also disclosed (for example, Patent Document 4). All of these are insufficient to achieve high saturation.

JP 2005-157314 A JP 2007-286148 A Japanese Patent Laid-Open No. 2006-267641 JP 2006-154363 A

  The present invention has been made on the basis of the above circumstances, and an object of the present invention is to develop an electrostatic image having a high saturation color image having a vivid color tone without color turbidity and having excellent light resistance. Another object is to provide a toner and an image forming method.

  As a result of intensive studies, the present inventors have studied a novel colorant that can replace quinacridone pigments. I. It has been found that the use of Acid Red 52 solves the problems of the present invention.

  The electrostatic image developing toner of the present invention is an electrostatic image developing toner comprising toner particles containing at least a binder resin and a colorant, and the colorant constituting the toner particles is C.I. I. Acid Red 52 is contained.

The image forming method of the present invention comprises an electrostatic charge image developing yellow toner comprising yellow toner particles containing at least a binder resin and a yellow colorant;
A magenta toner for developing an electrostatic image comprising magenta toner particles containing at least a binder resin and a magenta colorant;
A cyan toner for developing an electrostatic image comprising cyan toner particles containing at least a binder resin and a cyan colorant;
An image forming method using a full color toner kit comprising at least four kinds of black toner for developing an electrostatic charge image comprising black toner particles containing at least a binder resin and a black colorant,
The magenta colorant is C.I. I. Acid Red 52 is contained.

  According to the toner for developing an electrostatic image of the present invention, C.I. I. By using Acid Red 52, a magenta toner image can be formed.

  According to the toner for developing an electrostatic image of the present invention, C.I. I. By using Acid Red 52, the formed color image has a vivid color tone with no turbidity, and the formed image has stable light resistance over a long period of time.

  Further, according to the image forming method of the present invention, in the image forming method using a full color toner kit comprising at least four kinds of toners, C.I. I. By using Acid Red 52, the primary color image formed by the electrostatic image developing magenta toner has a vivid color tone with no color turbidity. Therefore, the electrostatic image developing magenta toner and other colors The secondary color image formed by superimposing these color toners also has a vivid color tone.

1 is a schematic diagram illustrating an example of a configuration of an image forming apparatus used in the present invention.

[Toner for electrostatic image development]
The toner for developing an electrostatic charge image of the present invention comprises toner particles containing at least a binder resin and a colorant. I. Acid red 52 is contained.
The electrostatic image developing toner of the present invention can be used as an electrostatic image developing magenta toner (hereinafter also simply referred to as “magenta toner”) for forming a magenta toner image. And magenta toner particles containing at least a binder resin and a magenta colorant. The colorant constituting the magenta toner particles is C.I. I. It contains Acid Red 52 or this as a main component.

[Colorant]
The colorant constituting the toner particles according to the present invention is C.I. I. Acid red 52 is contained.
C. I. Acid Red 52 is a xanthene acid dye having excellent transparency, fluorescence, and excellent light stability.
The toner of the present invention has C.I. I. By using Acid Red 52, it is possible to form images with wider and more stable color reproducibility than conventional images using toners using colorants such as quinacridone pigments and images using printing inks. can do. In addition, since the light stability is excellent, the color stability is also excellent. In particular, when an image such as computer graphics having a wide color gamut is output on the display, an image having a color gamut close to the color gamut on the display can be formed.

  The toner of the present invention includes C.I. I. The content of Acid Red 52 is preferably 1 to 10% by mass in the toner, and more preferably 2 to 8% by mass. C. I. When the content of Acid Red 52 is less than 1% by mass, the coloring power of the toner may be insufficient. On the other hand, C.I. I. When the content of Acid Red 52 exceeds 10% by mass, the colorant is liberated or adhered to the carrier, which may affect the chargeability.

  When the toner of the present invention is used as a magenta toner, C.I. I. In addition to Acid Red 52, a naphthol pigment or the like can be contained as a color tone adjustment. In this case, the content of the naphthol pigment is C.I. I. It is preferable to be less than 50% by mass with respect to Acid Red 52. When the content of the naphthol pigment exceeds 50% by mass, there is a possibility that color turbidity may occur in the formed image.

  Specific examples of naphthol pigments include C.I. I. Pigment red 112, C.I. I. Pigment Red 146, Permanent Carmine FBB02, C.I. I. Pigment red 170 and the like.

In the present invention, C.I. I. The acid red 52 is preferably dispersed in the toner particles in a number average primary particle size of about 10 to 300 nm.
The number average primary particle size is a colorant obtained by observing 10 toner particles by measuring the diameter of the colorant particles in the ferret direction using a photograph in which the cross section of the toner particles is magnified 50,000 times with a transmission electron microscope. The arithmetic average diameter of the particle diameter is defined as the number average primary particle diameter.

[Particle size of toner particles]
The toner particles constituting the toner according to the present invention preferably have a volume-based median diameter (D50v) of 3 μm or more and 8 μm or less. By setting the volume-based median diameter within the above range, it is possible to faithfully reproduce a very minute dot image at a level of 1200 dpi (dpi; number of dots per inch (2.54 cm)), for example.
Furthermore, by setting the volume-based median diameter to a small diameter level within the above range, the dots constituting the photographic image are miniaturized and a high-definition photographic image can be obtained. In particular, in a printing field called “on-demand printing” in which orders are received at a level of several hundred to several thousand copies, a printed matter containing high-definition photographic images can be quickly delivered to the user.

The volume-based median diameter (D50v) can be measured and calculated using a device in which a computer system for data processing is connected to “Multisizer 3” (manufactured by Beckman Coulter, Inc.).
As a measurement procedure, 0.02 g of a sample (toner) was added to 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of toner dispersion). Then, ultrasonic dispersion is performed for 1 minute to prepare a sample dispersion. Pipet this sample dispersion into a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in the sample stand until the measured concentration reaches 5 to 10%, and set the measuring machine count to 2500. To measure. The aperture size of the multisizer 3 is 50 μm.

[Particle size distribution of toner particles]
The toner particles according to the present invention preferably have a coefficient of variation (CV value) in the volume-based particle size distribution of 2% to 21%, more preferably 5% to 15%.
The coefficient of variation (CV value) in the volume-based particle size distribution represents the degree of dispersion in the particle size distribution of the toner particles on the volume basis and is defined by the following equation.
Formula) CV value (%) = (standard deviation in number particle size distribution) / (median diameter in number particle size distribution (D50v)) × 100
The smaller the CV value, the sharper the particle size distribution, meaning that the toner particles have the same size. That is, when the CV value is in the above range, toner particles having a uniform size can be obtained, so that fine dot images and fine lines required in digital image formation can be reproduced with higher accuracy. Is possible. Further, in the case of forming a photographic image, it is possible to form a high-quality photographic image of an image level produced by printing ink or higher by using small-diameter toner having a uniform size.

[Toner softening point temperature]
The toner according to the present invention preferably has a softening point temperature (Tsp) of 70 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower. The colorant used in the toner according to the present invention has a stable property in which the spectrum does not change even under the influence of heat. Therefore, it is possible to further reduce the influence of heat applied to the colorant, and therefore, it is possible to form an image without imposing a burden on the colorant.
Further, by setting the softening point temperature of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, so that the power consumption is reduced and the burden on the environment can be reduced.

The softening point temperature of the toner can be controlled by, for example, the following methods alone or in combination of two or more.
(1) A method of adjusting the type and composition ratio of monomers used for forming the binder resin.
(2) A method of adjusting the molecular weight of the binder resin according to the type and amount of chain transfer agent.
(3) A method of adjusting the type and addition amount of wax and the like.

Further, the method for measuring the softening point temperature of the toner is specifically a “flow tester CFT-500” (manufactured by Shimadzu Corporation), which is molded into a columnar shape with a height of 10 mm, and the temperature rising rate is 6 ° C./min. While being heated, a pressure of 1.96 × 10 ⁶ Pa is applied from the plunger, and the pressure is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm. Thereby, a curve between the plunger drop amount and temperature of the flow tester (softening flow curve) ), The first flowing temperature is the melting start temperature, and the temperature with respect to the drop of 5 mm is the softening point temperature.

[Toner Production Method]
The toner according to the present invention is composed of particles containing at least a binder resin and a colorant (hereinafter also referred to as “colored particles”). The method for producing the toner according to the present invention is not particularly limited, and can be produced by a conventional toner production method. That is, a so-called pulverization method for producing a toner through a kneading, pulverization, and classification process, a so-called pulverization method for polymerizing a polymerizable monomer, and at the same time, forming a particle while controlling the shape and size of a so-called polymerized toner. It can be produced by applying a production method (for example, emulsion polymerization method, suspension polymerization method, polyester elongation method, etc.).

  In the case of producing the toner according to the present invention by a pulverization method, it is preferable to produce the kneaded product while maintaining the temperature of the kneaded material at 130 ° C. or lower. This is because when the temperature applied to the kneaded product exceeds 130 ° C., the colorant aggregation state in the kneaded product varies due to the action of heat applied to the kneaded product, and the uniform aggregated state may not be maintained. Because. If variations occur in the aggregated state, the color tone of the produced toner varies, which may cause color turbidity.

  Next, the binder resin, wax and the like constituting the toner particles according to the present invention will be described with specific examples.

  First, the binder resin constituting the toner particles according to the present invention is not particularly limited, but is a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below. The union is a typical example. The polymer constituting the binder resin is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone or in a plurality of types. It can be set as the polymer produced combining.

Specific examples of vinyl polymerizable monomers are shown below.
For example,
(1) Styrene or styrene derivatives Styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-chloro styrene, 3,4-dichloro styrene, p-phenyl styrene, p-ethyl styrene 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, etc. (2) Methacrylic acid ester derivatives Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate , Lauryl methacrylate , Phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, etc. (3) Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate , N-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc. (4) olefins ethylene, propylene, isobutylene, etc. (5) vinyl esters vinyl propionate, vinyl acetate, benzoe (6) Vinyl ethers, vinyl methyl ether, vinyl ethyl ether, etc. (7) Vinyl ketones, vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. (8) N-vinyl compounds - vinylcarbazole, N- vinyl indole, vinyl compounds such as N- vinylpyrrolidone (9) Other vinyl naphthalene, vinyl pyridine, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives of acrylamide.

  Moreover, what has the ionic dissociation group shown below can also be used for the vinyl-type polymerizable monomer which comprises binder resin.

  First, examples of those having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. Examples of those having a sulfonic acid group include styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc., and those having a phosphoric acid group include acid phosphooxyethyl. And methacrylate.

Moreover, it is also possible to produce a binder resin having a crosslinked structure by using the polyfunctional vinyls shown below. Specific examples of polyfunctional vinyls are shown below.
Examples include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like. .

The toner particles according to the present invention can contain a wax. Specific examples include the following known ones.
For example,
(1) Polyolefin wax Polyethylene wax, polypropylene wax, etc. (2) Long chain hydrocarbon wax, paraffin wax, sazol wax, etc. (3) Dialkyl ketone wax, distearyl ketone, etc. (4) Ester wax Carnauba wax, Montan Wax, trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecanediol di Stearate, trimellitic trimellitic acid, distearyl maleate, etc. (5) Amide wax Ethylenediamine dibehenyl amide, trimellitic acid triste Riruamido, and the like.

  The melting point of the wax is usually 40 to 125 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable image formation can be performed without causing a cold offset or the like even when fixing at a low temperature. The wax content in the toner is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  In the toner of the present invention, particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm can be added as an external additive (hereinafter referred to as “external additive”) in the production process. .

By adding an external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of external additive is not particularly limited, and examples thereof include inorganic fine particles, organic fine particles, and a lubricant.
As the inorganic fine particles, conventionally known fine particles can be used. For example, silica, titania, alumina, strontium titanate fine particles and the like are preferable. Moreover, what hydrophobized these inorganic fine particles as needed can also be used.

Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150 manufactured by Hoechst, H -200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation.
As titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc. are mentioned.
Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specific examples include homopolymers such as styrene and methyl methacrylate and copolymers thereof.

  A lubricant can be added to the toner according to the present invention in order to further improve the cleaning property and the transfer property. Specific examples include higher fatty acid metal salts. Higher fatty acid metal salts include zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, manganese, iron, copper, magnesium, etc., zinc palmitate, copper, magnesium, calcium And the like, salts of zinc linoleic acid, calcium and the like, salts of zinc ricinoleic acid, calcium and the like.

  The addition amount of the external additive and the lubricant as described above is preferably 0.1 to 10.0% by mass with respect to the whole toner. Examples of methods for adding external additives and lubricants include methods using various known mixing devices such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

The toner according to the present invention can be used as a two-component developer composed of a carrier and a toner, or as a non-magnetic one-component developer composed only of a toner.
When the toner according to the present invention is used as a two-component developer, a full-color image can be formed at high speed using, for example, a tandem type image forming apparatus described later.

  Further, carriers that are magnetic particles used when used as a two-component developer are conventionally known, for example, metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead. It is possible to use materials. Among these, ferrite particles are preferable.

  The volume average particle size of the carrier is preferably 15 to 100 μm, more preferably 25 to 80 μm.

  When the toner is used as a non-magnetic one-component developer that forms an image without using a carrier, the toner is slid and pressed against the charging member and the developing roller surface during image formation. Image formation by the non-magnetic one-component development method can simplify the structure of the developing device, and thus has an advantage that the entire image forming device can be made compact. Therefore, when the toner according to the present invention is used as a non-magnetic one-component developer, a full-color image can be formed by a compact image forming apparatus, and a full-color image having excellent color reproducibility can be obtained even in a space-limited working environment. Formation is possible.

(Image forming method)
The image forming method of the present invention can form a full color image by using a full color toner kit comprising at least four kinds of toners.

[Full Color Toner Kit]
The full-color toner kit according to the present invention comprises an electrostatic charge image developing yellow toner (hereinafter also simply referred to as “yellow toner”), an electrostatic charge image developing magenta, comprising toner particles containing at least a binder resin and a colorant. Toner (hereinafter also simply referred to as “magenta toner”), cyan toner for developing electrostatic images (hereinafter also simply referred to as “cyan toner”) and black toner for developing electrostatic images (hereinafter simply referred to as “black toner”) The colorant used in the magenta toner is C.I.). I. Acid red 52 is contained.

[Yellow colorant]
Specific examples of the yellow colorant for yellow toner used in the full color toner kit according to the present invention include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, etc. can be used, and mixtures thereof can also be used.

[Cyan colorant]
Specific examples of the cyan colorant for cyan toner used in the full color toner kit according to the present invention include C.I. I. Pigment Blue 15: 3 can be used.

[Black colorant]
As the colorant for the black toner used in the full color toner kit according to the present invention, specifically, carbon black, magnetic material, titanium black and the like can be used, and as the carbon black, channel black, furnace black, acetylene black, etc. Thermal black, lamp black, etc. are used. Magnetic materials include ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but exhibit ferromagnetism by heat treatment, For example, a kind of alloy called Heusler alloy such as manganese-copper-aluminum and manganese-copper-tin, chromium dioxide, and the like can be used.

  These yellow colorant, cyan colorant and black colorant are preferably dispersed in the toner particles with a number average primary particle diameter of about 10 to 200 nm.

  The content of these colorants is preferably 1 to 10% by mass in the toner, and more preferably 2 to 8% by mass. When the content of the colorant is less than 1% by mass, the coloring power of the toner may be insufficient. On the other hand, when the content of the colorant exceeds 10% by mass, the colorant is liberated or adhered to the carrier, which may affect the chargeability.

[Magenta colorant]
Examples of the magenta colorant for the magenta toner used in the full color toner kit according to the present invention include C.I. I. It is set as the structure containing the acid red 52, and can be set as the structure similar to the magenta colorant mentioned above.

  Yellow toner, cyan toner and black toner using these colorants and C.I. I. A full color image can be formed by using a full color toner kit composed of magenta toner containing Acid Red 52.

  Hereinafter, an image forming method when the toner according to the present invention is used as a two-component developer will be described.

FIG. 1 is a schematic diagram showing an example of the configuration of an image forming apparatus used in the present invention.
The image forming apparatus 40 is a tandem full-color image forming apparatus, and includes a plurality of image forming units 50Y, 50M, 50C, and 50K provided along a belt-like intermediate transfer member 46, a paper feed cassette 42, and the like. And a fixing device 49. In FIG. 1, reference numeral 41 denotes an operation unit, and reference numerals 47Y, 47M, 47C, and 47K denote toner cartridges for respective colors.

  The image forming unit 50Y forms a yellow toner image, and includes a photoreceptor 51Y. Around the photoreceptor 51Y, a charging unit 52Y, an exposure unit 53Y, a developing device 54Y, a primary transfer unit 57Y, and a cleaning unit are provided. The means 58Y is arranged and configured.

The image forming units 50M, 50C, and 50K have the same configuration as that of the image forming unit 50Y, except that magenta, cyan, and black toner images are formed instead of forming yellow toner images.
Here, a yellow toner image is formed by the image forming unit 50Y, a magenta toner image is formed by the image forming unit 50M, and a cyan toner image is formed by the image forming unit 50C. According to the image forming unit 50K, a black toner image is formed.

  The intermediate transfer member 46 is stretched around a plurality of support rollers 46A, 46B, and 46C, and is supported so as to be able to circulate.

In this image forming apparatus 40, the toner images of the respective colors formed by the image forming units 50Y, 50M, 50C, and 50K are sequentially transferred onto the intermediate transfer body 46 that circulates by the primary transfer units 57Y, 57M, 57C, and 57K. Primary transfer is performed and superimposed to form a color toner image.
On the other hand, the image support P accommodated in the paper feed cassette 42 is fed one by one by the paper feed roller 43, conveyed to the secondary transfer means 57A by the registration roller 44, and the color support on the image support P. The toner image is secondarily transferred.
Next, the image support P is conveyed to the fixing device 49 and subjected to a fixing process. Thereafter, the image support P is sandwiched between the discharge rollers 45 and discharged onto the discharge tray 48 outside the apparatus.

  Further, after the color toner image is transferred to the image support P by the secondary transfer means 57A, the residual toner is removed by the cleaning means 59 from the intermediate transfer body 46 from which the image support P has been separated by curvature.

  The image forming method of the present invention is not limited to the above-described image forming method by the image forming apparatus, and can be formed by, for example, an image forming apparatus using a nonmagnetic one-component developer.

  According to the present invention, C.I. I. By using Acid Red 52, the formed color image has a vivid color tone with no turbidity, and the formed image has stable light resistance over a long period of time.

  According to the present invention, in the image forming method using a full-color toner kit comprising at least four kinds of toners, C.I. I. By using Acid Red 52, the primary color image formed by the electrostatic image developing magenta toner has a vivid color tone with no color turbidity. Therefore, the electrostatic image developing magenta toner and other colors The secondary color image formed by superimposing these color toners also has a vivid color tone.

  Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

[Magenta Toner Preparation Example 1: Preparation of Toner by Kneading / Crushing Method]
The following toner composition was put into a “Henschel mixer” (manufactured by Mitsui Miike Mining Co., Ltd.), and the peripheral speed of the stirring blade was set to 25 m / second and mixed for 5 minutes.
Polyester resin 100 parts by mass (bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid condensate weight average molecular weight 20,000)
・ C. I. Acid Red 52 5 parts by mass Wax (pentaerythritol tetrastearate) 6 parts by mass Charge control agent (boron dibenzylate) 1 part by mass After kneading the mixture with a twin-screw extrusion kneader and then roughly pulverizing with a hammer mill The magenta toner particles having a volume-based median diameter of 5.5 μm are obtained by pulverizing with a “turbomill pulverizer” (manufactured by Turbo Kogyo Co., Ltd.) and further by fine powder classification with an airflow classifier utilizing the Coanda effect. 1] was obtained.
Next, the following external additives were added to the magenta toner particles [1], and external addition processing was performed with a Henschel mixer to prepare magenta toner [1].
-Hexamethylsilazane-treated silica (number-average primary particle size 12 nm) 0.6 parts by mass-N-octylsilane-treated titanium dioxide (number-average primary particle size 24 nm) 0.8 parts by mass Was performed under the conditions of a peripheral speed of the stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

[Magenta Toner Preparation Example 2: Preparation of Toner by Emulsion Association Method]
(1) Preparation of Colorant Fine Particle Dispersion [1] 11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, and dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, C.I. I. 4 parts by mass of Acid Red 52 are gradually added, and dispersion processing is performed using “Clearmix W Motion CLM-0.8” (manufactured by M Technique Co., Ltd.), and a colorant containing colorant fine particles [1] A fine particle dispersion [1] was prepared.
The colorant fine particles [1] had a volume-based median diameter of 98 nm. The volume-based median diameter was measured under the following measurement conditions using “MICROTRAC UPA-150” (manufactured by HONEYWELL).
Sample refractive index 1.59
・ Sample specific gravity 1.05 (in terms of spherical particles)
Solvent refractive index 1.33
Solvent viscosity 0.797 Pa · s (30 ° C), 1.002 Pa · s (20 ° C)
-Zero point adjustment Prepared by adding ion-exchanged water to the measurement cell.

(2) Preparation of core part resin particles [1] Core part resin particles [1] having a multilayer structure were prepared through the following first stage polymerization, second stage polymerization, and third stage polymerization.
(A) First-stage polymerization 4 parts by mass of an anionic surfactant represented by the following structural formula (1) are charged together with 3040 parts by mass of ion-exchanged water into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device. Then, a surfactant aqueous solution was prepared.
Structural formula (1) C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
A polymerization initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 400 parts by mass of ion-exchanged water was added to the surfactant aqueous solution, and the temperature was raised to 75 ° C. The resulting monomer mixture was dropped into the reaction vessel over 1 hour.
-Styrene 532 parts by mass-n-butyl acrylate 200 parts by mass-methacrylic acid 68 parts by mass-n-octyl mercaptan 16.4 parts by mass After the above monomer mixture was added dropwise, the system was heated at 75 ° C for 2 hours. Then, polymerization (first stage polymerization) was carried out by stirring to produce resin particles [A1]. The weight average molecular weight of the resin particles [A1] prepared by the first stage polymerization was 16,500.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was charged into a flask equipped with a stirrer, followed by paraffin wax “HNP-57” (manufactured by Nippon Seiwa Co., Ltd.) 93.8 as a wax. A part by mass was added and heated to 90 ° C. to dissolve. In this way, a monomer solution was prepared.
Styrene 101.1 parts by mass n-butyl acrylate 62.2 parts by mass Methacrylic acid 12.3 parts by mass n-octyl mercaptan 1.75 parts by mass On the other hand, 3 parts by mass of the anionic surfactant is ion-exchanged water. A surfactant aqueous solution dissolved in 1560 parts by mass was prepared and heated to 98 ° C. After adding 32.8 parts by mass (in terms of solid content) of resin particles [A1] to this surfactant aqueous solution, and further adding the monomer solution containing the paraffin wax, mechanical dispersion having a circulation route is added. It was mixed and dispersed for 8 hours with a machine “CLEAMIX” (manufactured by M Technique). An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared by the mixing and dispersing.
Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to the emulsified particle dispersion, and the system is polymerized by heating and stirring at 98 ° C. for 12 hours. (Second stage polymerization) was performed to prepare resin particles [A2]. The weight average molecular weight of the resin particles [A2] produced by the second stage polymerization was 23,000.

(C) Third-stage polymerization To the resin particles [A2] obtained by the second-stage polymerization, a polymerization initiator solution in which 5.45 parts by mass of potassium persulfate is dissolved in 220 parts by mass of ion-exchanged water is added, Under a temperature condition of 80 ° C., a monomer mixed solution composed of the following compounds was added dropwise over 1 hour.
-Styrene 293.8 parts by mass-n-Butyl acrylate 154.1 parts by mass-n-octyl mercaptan 7.08 parts by mass After completion of dropping, the mixture is heated and stirred for 2 hours to perform polymerization (third stage polymerization). After completion, the mixture was cooled to 28 ° C. to produce core part resin particles [1]. Prepared by third stage polymerization. The weight average molecular weight of the core part resin particles [1] was 26,800.

(3) Production of resin particles for shell [1] Polymerization was carried out in the same manner except that the monomer mixture used in the first stage polymerization in the production of resin particles for core [1] was changed to the following. Resin and post-reaction treatments were performed to produce shell resin particles [1].
-Styrene 624 mass parts-2-ethylhexyl acrylate 120 mass parts-Methacrylic acid 56 mass parts-n-octyl mercaptan 16.4 mass parts

(4) Preparation of magenta toner [2] (a) Formation of core part [1] In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device,
・ Core part resin particles [1] 420.7 parts by mass (solid content conversion)
-900 parts by mass of ion exchange water-Colorant fine particle dispersion [1] 200 parts by mass were charged and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.
Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using “Multisizer 3” (manufactured by Beckman Coulter), and when the volume-based median diameter of the associated particles became 5.5 μm, 40.2 mass of sodium chloride was obtained. The solution was dissolved in 1000 parts by mass of ion-exchanged water to stop the association.
After the association was stopped, the core temperature [1] was produced by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.
It was 0.912 when the average circularity of core part [1] was measured using "FPIA2000" (made by Systex).

(B) Formation of shell layer Next, 96 parts by mass of the resin particles [1] for shell are added at 65 ° C., and 2 parts by mass of magnesium chloride hexahydrate is added to 1000 parts by mass of ion-exchanged water. After adding the aqueous solution dissolved in 10 minutes, the mixture was heated to 70 ° C. and stirred for 1 hour. In this manner, the shell resin particles [1] were fused to the surface of the core [1], and then aged at 75 ° C. for 20 minutes to form a shell.
Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the particles produced by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Magenta toner particles [2] having a layer were prepared.

(C) External Addition Treatment The following external additive was added to the produced magenta toner particles [2], and external addition treatment was performed with a Henschel mixer to produce magenta toner [2].
-Hexamethylsilazane-treated silica (number-average primary particle size 12 nm) 0.6 parts by mass-N-octylsilane-treated titanium dioxide (number-average primary particle size 24 nm) 0.8 parts by mass Was performed under the conditions of a peripheral speed of the stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

[Comparative Magenta Toner Preparation Example 1]
A comparative magenta toner [1] was prepared in the same manner as in Magenta Toner Preparation Example 1, except that “CI Pigment Red 122” was used instead of “CI Acid Red 52”.

[Comparative Magenta Toner Preparation Example 2]
A comparative magenta toner [2] was prepared in the same manner as in Magenta Toner Preparation Example 2, except that “CI Pigment Red 122” was used instead of “CI Acid Red 52”.

[Yellow toner preparation example 1]
A yellow toner [1] was prepared in the same manner except that “CI Pigment Yellow 74” was used instead of “CI Acid Red 52” in Magenta Toner Preparation Example 1.

[Yellow toner preparation example 2]
A yellow toner [2] was prepared in the same manner except that “CI Pigment Yellow 74” was used instead of “CI Acid Red 52” in Magenta Toner Preparation Example 2.

[Cyan toner production example 1]
Cyan toner [1] was prepared in the same manner except that “CI Pigment Blue 15: 3” was used instead of “CI Acid Red 52” in Magenta Toner Preparation Example 1.

[Cyan toner preparation example 2]
Cyan toner [2] was prepared in the same manner except that “CI Pigment Blue 15: 3” was used instead of “CI Acid Red 52” in Magenta Toner Preparation Example 2.

[Black toner production example 1]
A black toner [1] was prepared in the same manner as in Magenta Toner Preparation Example 1 except that “Carbon Black: Mogal L” was used instead of “CI Acid Red 52”.

[Black toner production example 2]
A black toner [2] was prepared in the same manner as in Magenta Toner Preparation Example 2, except that “Carbon Black: Mogal L” was used instead of “CI Acid Red 52”.

(Preparation of developer)
The magenta toner [1], [2], comparative magenta toner [1], [2], yellow toner [1], [2], cyan toner [1], [2] and black toner [1], [2] 2] is mixed with a ferrite carrier having a volume average particle diameter of 50 μm coated with methyl methacrylate and cyclohexyl methacrylate resin, and a magenta developer [1], [2] having a toner concentration of 6%, and a comparative magenta developer [ 1], [2], yellow developers [1], [2], cyan developers [1], [2] and black developers [1], [2] were prepared.

[Examples 1 and 2 and Comparative Examples 1 and 2]
The developers shown in Table 1 were loaded into a commercially available composite printer “bizhub Pro C500” (manufactured by Konica Minolta Business Technologies, Inc.) corresponding to the image forming apparatus shown in FIG. .

(Evaluation of color reproduction range of full color image)
Solid images of yellow (Y), magenta (M), cyan (C), red (R), blue (B) and green (G) in an environment of temperature 20 ° C. and humidity 50% RH (2 cm × 2 cm) was formed, and its color gamut was expressed in a ^* -b ^* coordinates, and the area was measured. The color reproduction range was evaluated with the area constituted by the Y / M / C / R / B / G color gamut of Comparative Example 1 being 100. The results are shown in Table 1.

(Evaluation of light resistance)
A 10 cm × 10 cm magenta image was formed, and this image was irradiated for 480 hours under irradiation conditions of a xenon lamp of 70,000 lux using “Xenon Weather Meter XL75” (manufactured by Suga Test Instruments Co., Ltd.). The change rate of the reflection density was measured. The results are shown in Table 1.

    As described above, according to the example of the present invention, it was confirmed that the color reproduction range can be expanded as compared with the comparative example and an image excellent in light resistance can be formed.

40 Image forming apparatus 41 Operation unit 42 Paper feed cassette 43 Paper feed roller 44 Registration roller 45 Paper discharge roller 46 Intermediate transfer members 46A, 46B, 46C Support rollers 47Y, 47M, 47C, 47K Toner cartridge 48 Paper discharge tray 49 Fixing device 50Y , 50M, 50C, 50K Image forming unit 51Y Photoconductor 52Y Charging means 53Y Exposure means 54Y Developing device 57Y Primary transfer means 57A Secondary transfer means 58Y Cleaning means 59 Cleaning means P Image support

Claims (2)

An electrostatic charge image developing toner comprising toner particles containing at least a binder resin and a colorant,
The colorant constituting the toner particles is C.I. I. An electrostatic charge image developing toner comprising Acid Red 52. A yellow toner for developing an electrostatic image comprising yellow toner particles containing at least a binder resin and a yellow colorant;
A magenta toner for developing an electrostatic image comprising magenta toner particles containing at least a binder resin and a magenta colorant;
A cyan toner for developing an electrostatic image comprising cyan toner particles containing at least a binder resin and a cyan colorant;
An image forming method using a full color toner kit comprising at least four kinds of black toner for developing an electrostatic charge image comprising black toner particles containing at least a binder resin and a black colorant,
The magenta colorant is C.I. I. An image forming method comprising Acid Red 52.