JP2009180980A - Toner for developing electrostatic charge image, and developer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for developing an electrostatic charge image and a developer, capable of forming a secondary color toner image of high saturation having excellent light stability and capable of matching a hue angle thereof to color regeneration of a photograph image, in the full-colored image of high saturation having a brilliant color tone with no color muddiness. <P>SOLUTION: This toner for developing the electrostatic charge image contains at least a binding resin and a coloring agent, and the coloring agent contains silicon phthalocyanine or silicon naphthalocyanine, in the toner for developing the electrostatic charge image and the developer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner and developer used for electrophotographic image formation, and more specifically, in an electrostatic charge image developing toner containing a phthalocyanine compound in a colorant, having a structure as a coloring material. The present invention relates to an electrostatic charge image developing toner and developer containing two different types of silicon phthalocyanine compounds.

  Electrophotographic image formation using toner for developing electrostatic images (hereinafter also simply referred to as toner) has recently become capable of full-color printing in addition to monochrome printing typified by conventional document creation. . Since such a full-color image forming apparatus can produce the required number of printed materials on demand without causing a plate like printing, it is mainly used in the light printing field where there are many opportunities to order small quantities of prints. (For example, see Patent Document 1).

  When producing full-color prints such as catalogs and advertisements with toner, the toner used is required to have color reproducibility so that an image faithful to the original can be obtained. In other words, in full-color image formation, yellow, magenta, and cyan toner images are superimposed to reproduce the target tone image, and these color toners that serve as a base for achieving faithful color reproduction have good color reproducibility. It was required to have.

  Therefore, for the purpose of improving the color reproducibility of color toners, studies have been made on colorants including various metal complex dyes.

  For example, one of typical color toner colorants is a copper phthalocyanine pigment. Toners using copper phthalocyanine pigments are versatile and have excellent light resistance, but the baseline on the long wavelength side is high in the reflection spectrum of the image, and there is a tendency to form an image with a hue that makes color turbidity felt. It was observed. Therefore, it is said that it is not suitable for image formation that requires high color reproducibility, which is typified by printing of company logo marks.

  Thus, development of a toner that does not cause color turbidity by improving the copper phthalocyanine pigment has been studied (see, for example, Patent Document 2), but has not yet been sufficiently resolved.

In addition, a toner using a pigment such as a copper phthalocyanine-based pigment has versatility to obtain image-level image quality produced with printing ink, but it is difficult to develop an optimum hue angle for color reproduction of a photographic image. It was. Therefore, a toner containing a colorant capable of expressing a hue angle optimum for color reproduction of a photographic image instead of a copper phthalocyanine pigment has been studied (for example, see Patent Documents 2 and 3).
JP 2005-157314 A JP-A-5-239368 JP 2006-63171 A

  An object of the present invention is to provide a toner for developing an electrostatic image having a high-saturation full-color image having a vivid color tone free of color turbidity and having excellent light resistance. In particular, an object of the present invention is to provide a toner for developing an electrostatic image that can adjust the hue angle to the color reproduction of a photographic image and can form a secondary color toner image with high saturation. It is another object of the present invention to provide an electrostatic charge developing toner and a developer having further improved performance by containing two types of silicon phthalocyanine compounds having different structures.

  The above object of the present invention can be achieved by the following configuration.

  1. An electrostatic charge image developing toner comprising at least a binder resin and a colorant, wherein the colorant is represented by the following general formulas (1) and (2): An electrostatic charge image developing toner comprising phthalocyanine.

(In the formula, A ₁₁ , A ₁₂ , A ₁₃ and A ₁₄ represent a benzene ring or a naphthalene ring. R ₁ , R ₂ , R ₃ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a substituent. Represents.)

(In the formula, A ₂₁ , A ₂₂ , A ₂₃ and A ₂₄ represent a benzene ring or a naphthalene ring. R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a substituent.)
2. The content of the compound represented by the general formula (2) is 0.1 to 10.0% by mass in the total amount of the compound of the general formula (1) and the compound of the general formula (2). 2. The toner for developing an electrostatic charge image according to 1 above.

3. R ₁ , R ₂ , R ₃ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ in the general formula (1) and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ in the general formula (2) are halogens. Atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, quaternized heterocyclic groups containing nitrogen atoms, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, carboxy groups or the like Salt, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, Carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, amino group, acyl group Mino group, sulfonamide group, ureido group, thioureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, sulfonylureido group, acylureido group , Acylsulfamoylamino group, nitro group, mercapto group, thio group, sulfonyl group, sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoric acid amide 3. The electrostatic image developing toner according to 1 or 2, wherein the toner is one selected from a group having a phosphate ester structure, a silyloxy group, and a silyl group.

4). 4. The electrostatic image developing toner according to any one of 1 to 3, wherein R ₁ , R ₂ and R ₃ in the general formula (1) are alkyl groups having 1 to 4 carbon atoms. .

  5). 5. A developer using the electrostatic image developing toner according to any one of 1 to 4 above.

  According to the developer using the toner for developing an electrostatic charge image according to the present invention, a full color image having high saturation without color turbidity can be obtained, and the formed toner image can exhibit stable light resistance over a long period of time. became. In addition, since a single color toner image excellent in color without turbidity can be obtained, the secondary color formed using the toner according to the present invention also has a vivid color tone. Furthermore, improvement in color makes it possible to match the hue angle of the toner with the color reproduction of the photographic image. In addition, better performance can be obtained with respect to chargeability and offset resistance.

  The present invention will be described in more detail.

  The present invention relates to a toner for developing an electrostatic image comprising at least a resin and a colorant, and a developer using the toner, and in particular, a good color tone such that the hue angle of the toner can be matched to the color reproduction of a photographic image. And an electrostatic charge image developing toner having stable light resistance.

  With the toner according to the present invention, a good color tone without color turbidity can be expressed. The reason why such a good color tone can be expressed is presumably because the crystallinity of the colorant is weak compared to conventional products such as copper phthalocyanine pigments. That is, the low crystallinity facilitates uniform dispersion of the colorant in the toner particles. As a result, when the toner melts at the time of fixing, the colorant is uniformly dispersed on the transfer sheet, so that it is presumed that a color tone image without color turbidity can be obtained. In addition, when a secondary color toner image is formed, it is presumed that a secondary color having no turbidity can be obtained because it can be uniformly dispersed with a multicolored colorant.

  Also, higher solubility can be obtained by lowering the crystallinity. For example, in the case of producing a toner by a polymerization method, the dispersion in the polymerizable monomer and the resin particle dispersion at the time of association It is presumed that the dispersibility in the toner is improved and the colorant is uniformly dispersed in the toner particles.

  In addition, the toner according to the present invention exhibits sufficient color tone by dispersing the colorant uniformly in the toner particles or on the fixed image as described above, and the colorant molecule itself has a stable structure. It is presumed that light resistance can be expressed.

  Further, since the colorant is easily dispersed uniformly in the toner particles or on the fixed image, a high molecular extinction coefficient is expected, and a sufficient image density can be obtained with a small amount of colorant. As a result, it is considered possible to suppress toner consumption during image formation.

  In addition, although detailed factors are unclear, the electrostatic charge developing toner having the configuration of the present invention can further improve the performance such as chargeability and offset resistance.

  The electrostatic charge developing toner of the present invention is characterized by containing two kinds of compounds represented by the general formula (1) and the general formula (2) as colorants.

The compounds represented by the general formulas (1) and (2) will be described in more detail.
In the general formulas (1) and (2), R ₁ , R ₂ , R ₃ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ represent substituents.

  Examples of the substituent include a halogen atom (fluorine atom, chloro atom, bromine atom, or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, and active methine group), alkenyl group, alkynyl group, aryl Group, heterocyclic group (regardless of the position of substitution), heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group, imidazolio group, quinolinio group, or isoquinolinio group), acyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethylene Oxy group or propylene Aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or) Heterocycle) amino group, acylamino group, sulfonamido group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group Oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl, aryl) Or heterocyclic) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or salt thereof, phosphoric acid amide or phosphoric ester structure , A silyloxy group (for example, trimethylsilyloxy, and t-butyldimethylsilyloxy), a silyl group (for example, trimethylsilyl, t-butyldimethylsilyl, or phenyldimethylsilyl) and the like. These substituents may be further substituted with these substituents.

R ₁ , R ₂ and R ₃ are preferably an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, or an aryloxy group having 6 to 18 carbon atoms. More preferably an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms, and most preferably an alkyl group having 1 to 4 carbon atoms.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ are preferably hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, nitro group, alkylthio. Group, an arylthio group, more preferably a hydrogen atom, a chloro atom, an alkoxy group or a nitro group.

Further, in the compounds of the general formulas (1) and (2) which are simultaneously contained as a colorant in the electrostatic charge developing toner of the present invention, a substituent represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ and R _The substituents represented by ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ may be the same or different.

  Although the concrete structure of the compound represented by General formula (1) of this invention below is shown, this invention is not a thing limited by these.

  Although the specific structure of the compound represented by General formula (2) of this invention below is shown, this invention is not a thing limited by these.

  The compound represented by the general formula (2) of the present invention is a phthalonitrile compound or a 1,3-diiminoisoindoline compound as a starting material, and the silicon naphthalocyanine compound is a naphthalonitrile compound or 1, It can be obtained by reacting 3-diiminobenzisoindoline compound as a starting material with silicon tetrachloride in a high boiling point solvent. To synthesize with high purity, 1,3-diiminoisoindoline compound or 1,3 -It is common to use a diiminobenzisoindoline compound as a starting material and synthesize it using an appropriate catalyst. For example, it reacts with silicon tetrachloride using a non-polar solvent such as 1-chloronaphthalene, 1,2,3,4-tetrahydronaphthalene, trichlorobenzene, dichlorobenzene and the like with a high-boiling tertiary amine such as tri-n-butylamine as a catalyst. Alternatively, it can be obtained by reacting in a quinoline solvent without a catalyst.

  The compound represented by the general formula (2) of the present invention is obtained by reacting a silyl chloride having a desired substituent with the compound represented by the general formula (2) as a reaction intermediate in the presence of a base. be able to.

  Synthesis examples of the compounds represented by the general formulas (1) and (2) of the present invention will be described below, but the present invention is not limited thereto.

Synthesis Example Synthesis of Compound Example 1-2 (1) Synthesis of dichlorosilicon phthalocyanine 152.3 g of 1,3-diiminoisoindoline and 257.3 g of silicon tetrachloride were added to 1750 ml of quinoline, and 210 to 220 under a nitrogen atmosphere. The reaction was carried out at 1 ° C. for 1 hour. The product was filtered hot at 180 ° C. and washed with quinoline and acetone in this order. Subsequently, after heating and refluxing in 1000 ml of acetone, the crystals were filtered off and dried to obtain 141.5 g of dichlorosilicon phthalocyanine.

(2) Synthesis of Compound 2-1 140.0 g of dichlorosilicon phthalocyanine synthesized in (1) was added to a mixed solution of 35.0 g of NaOH, 3100 ml of water, and 830 ml of pyridine, and reacted for 1 hour under reflux heating. The product was filtered hot and washed with pyridine, acetone and water in this order. Subsequently, after stirring at room temperature several times in 1300 ml of water, neutrality was confirmed, and the crystals were filtered and dried to obtain 105.3 g of Compound 2-1.

(3) Synthesis of Compound 1-2 100.0 g of Compound 2-1 synthesized in (2) and 124.3 ml of tri-n-butylamine were added to 3000 ml of quinoline, and further 87.7 g of triethylsilyl chloride in a nitrogen atmosphere. And reacted at 140-150 ° C. for 6 hours. The product was cooled to room temperature and then added to a mixed solution of 6000 ml of methanol and 1600 ml of water. The precipitated crystals were separated by filtration, the crystals were heated and suspended in 2500 ml of toluene, cooled, filtered and dried to obtain 74.8 g of Compound 1-1.

  In the electrostatic charge developing toner of the present invention, among the total amount of the compound of the general formula (1) and the compound of the general formula (2) contained as a colorant, the content of the compound represented by the general formula (2) Although there is no limitation, in order to obtain a better color tone, the content of the compound of the general formula (2) is preferably 0.1 to 15.0% by mass, more preferably 0.5 to 10.0% by mass. %, And 1.0 to 7.0% by mass is most preferable.

Further, in the compounds of the general formulas (1) and (2) which are simultaneously contained as a colorant in the electrostatic charge developing toner of the present invention, a substituent represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ and R _The substituents represented by ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ may be the same or different.

  The toner according to the present invention can express a wider and more stable color reproducibility than a conventional toner image or an image using printing ink by using the above-described compound. In particular, in recent years, there are many cases where an image displayed on a computer screen is printed out, but since the color gamut of conventional color printing is much narrower than the color gamut of a computer display, the image on the display is printed out. There was a big difference in the color of the. However, by using the toner according to the present invention, a printed image closer to the color gamut of the computer display than before can be obtained. Thus, it can be said that the toner according to the present invention greatly contributes to the expansion of the color gamut in the printed image.

  Next, the particle diameter of the toner according to the present invention will be described.

  The toner according to the present invention preferably has a volume-based median diameter (D50v) of 3 μm or more and 8 μm or less. By setting the volume reference median diameter in the above range, for example, 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)).

  The toner according to the present invention is one of the problems to be able to faithfully reproduce the color of a photographic image. By making the volume-based median diameter a small diameter level in the above range, a photographic image can be formed. The dot image to be reduced is miniaturized, and a high-definition photographic image equivalent to or better than the printed image is obtained. In particular, in a printing field called “on-demand printing” where a print order is received at a level of several hundred to several thousand copies, high-quality prints containing high-definition photographic images can be quickly delivered to the user.

  The volume-based median diameter (D50v diameter) of toner 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).

  As a measurement procedure, 0.02 g of toner is blended with 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 dispersing the toner). After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is injected into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand with a pipette until a measurement concentration of 5 to 10% is reached, and the measuring machine count is set to 2500. To do. The aperture size of the multisizer 3 is 50 μm.

  The toner according to the present invention preferably has 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.

CV value (%) = (standard deviation in number particle size distribution) / (median diameter (D50v) in number particle size distribution) × 100
The smaller the CV value, the sharper the particle size distribution, and the larger the toner particle size. In other words, since toners with uniform sizes can be obtained, it is possible to reproduce a fine dot image and fine lines required for digital image formation with higher accuracy. Further, when printing a photographic image, it is possible to produce a high-quality photographic image of an image level made with printing ink or higher by using small-diameter toners having a uniform size.

  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 compound used in the toner according to the present invention has a stable property that the spectrum does not change even under the influence of heat, but is added to the toner at the time of fixing by setting the softening point in the above range. The influence of heat can be further reduced. Therefore, since image formation can be performed without imposing a burden on the compound, it is expected to develop a wider and more stable color reproducibility.

  In addition, by setting the softening point of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, and environmentally friendly image formation with reduced power consumption can be realized.

The softening point of the toner can be controlled by, for example, the following methods alone or in combination. That is,
(1) The type and composition ratio of monomers used for resin formation are adjusted.
(2) The molecular weight of the resin is adjusted according to the type and amount of chain transfer agent.
(3) Adjust the type and amount of wax.

Further, the method for measuring the softening point temperature of the toner is specifically “Flow Tester CFT-500 (manufactured by Shimadzu Corporation)”, molded into a columnar shape with a height of 10 mm, and at a heating rate of 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) ), And the temperature at the first outflow is the melting start temperature, and the temperature for the drop of 5 mm is the softening point temperature.

  Next, a toner manufacturing method according to the present invention will be described.

  The toner according to the present invention is composed of particles (hereinafter also referred to as colored particles) containing at least a resin and a compound. The colored particles constituting the toner according to the present invention are not particularly limited, and can be produced by a conventional toner production method. That is, a toner manufacturing method by a so-called pulverization method in which a toner is prepared through a kneading, pulverization, and classification process, or a so-called polymerized toner in which a polymerizable monomer is polymerized and particles are formed while simultaneously controlling the shape and size. It can be produced by applying a production method (for example, an emulsion polymerization method, a suspension polymerization method, a polyester elongation method, etc.).

  When the toner according to the present invention is produced by a pulverization method, it is preferable to produce the toner while maintaining the temperature of the kneaded material at 130 ° C. or lower. This is because if the temperature applied to the kneaded product exceeds 130 ° C., the action of heat applied to the kneaded product may cause a change in the agglomeration state of the compound in the kneaded product, making it impossible to maintain a uniform aggregated state. It is. If variations occur in the aggregated state, the color tone of the produced toner varies, which may cause color turbidity.

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

  First, the resin that can be used in the toner according to the present invention is not particularly limited, but a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below is used. This is a typical example. The polymer constituting the resin that can be used in the present invention is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone. Or it is the polymer produced combining multiple types.

Specific examples of vinyl polymerizable monomers are shown below.
(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 , Lauric methacrylate (3) Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, acrylic acid, etc. Isobutyl, 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, (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 N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, etc. (9) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc. As the vinyl-based polymerizable monomer constituting the resin that can be used in the toner, those having an ionic dissociation group shown below can be used. Examples thereof include those having a functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain of the monomer, and specific examples thereof include the following.

  First, 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, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of those having a phosphoric acid group include acid phosphooxyethyl methacrylate. Is mentioned.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyls. Specific examples of polyfunctional vinyls are shown below.

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, etc. Next, the present invention Examples of the wax that can be used for the toner according to the present invention include the following known waxes.
(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 The melting point of Riruamido such as wax is usually from 40 to 125 ° C., preferably from 50 to 120 ° C., more preferably from 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 toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature. Further, 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.

  Next, the toner according to the present invention is prepared by adding particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm as external additives (= external additives) in the production process. Is possible.

  By adding the external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of the external additive is not particularly limited, and examples thereof include the following inorganic fine particles, organic fine particles, and lubricants.

  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 the 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. Specifically, homopolymers such as styrene and methyl methacrylate and copolymers thereof can be used.

  Further, a lubricant can be used to further improve the cleaning property and transfer property, and examples thereof include the following higher fatty acid metal salts. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid And salts of zinc and calcium of ricinoleic acid.

  The addition amount of these external additives and lubricants is preferably 0.1 to 10.0% by mass with respect to the whole toner. Examples of the method 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, for example, a full-color print can be produced at a high speed using a tandem image forming apparatus described later. In addition, by selecting a resin or a wax constituting the toner, it is possible to produce a full-color print compatible with so-called low-temperature fixing in which the paper temperature during fixing is about 100 ° C.

  In addition, 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 carrier has a volume average particle size of 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 print can be produced with a compact color printer, and a full-color print excellent in color reproducibility can be produced even in a space-limited work environment. Is possible.

  Next, an image forming method using the toner according to the present invention will be described. First, 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 view showing an example of an image forming apparatus that can be used when a toner according to the present invention is used as a two-component developer.

  In FIG. 1, 1Y, 1M, 1C and 1K are photoreceptors, 4Y, 4M, 4C and 4K are developing devices, 5Y, 5M, 5C and 5K are primary transfer rolls as primary transfer means, and 5A is a secondary transfer. Secondary transfer rolls as means, 6Y, 6M, 6C and 6K are cleaning devices, 7 is an intermediate transfer member unit, 24 is a heat roll type fixing device, and 70 is an intermediate transfer member.

  This image forming apparatus is called a tandem color image forming apparatus, and includes a plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an endless belt-shaped intermediate transfer body unit 7 as a transfer unit, and a recording member P. An endless belt-shaped sheet feeding / conveying means 21 and a heat roll type fixing device 24 as a fixing means. A document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.

  As one of the different color toner images formed on each photoconductor, an image forming unit 10Y that forms a yellow image includes a drum-shaped photoconductor 1Y as a first photoconductor, and a periphery of the photoconductor 1Y. A charging unit 2Y, an exposure unit 3Y, a developing unit 4Y, a primary transfer roll 5Y as a primary transfer unit, and a cleaning unit 6Y. An image forming unit 10M that forms a magenta image as another different color toner image is disposed around a drum-shaped photoconductor 1M as a first photoconductor, and the photoconductor 1M. A charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roll 5M as a primary transfer unit, and a cleaning unit 6M. In addition, an image forming unit 10C that forms a cyan image as one of other different color toner images is disposed around the photoconductor 1C as a drum-type photoconductor 1C as a first photoconductor. The charging unit 2C, the exposure unit 3C, the developing unit 4C, the primary transfer roll 5C as the primary transfer unit, and the cleaning unit 6C are provided. Further, an image forming unit 10K that forms a black image as one of other different color toner images is disposed around a drum-shaped photosensitive member 1K as a first photosensitive member, and the photosensitive member 1K. It has a charging means 2K, an exposure means 3K, a developing means 4K, a primary transfer roll 5K as a primary transfer means, and a cleaning means 6K.

  The endless belt-like intermediate transfer body unit 7 has an endless belt-like intermediate transfer body 70 as an intermediate transfer endless belt-like second image carrier that is wound around a plurality of rolls and is rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10K is sequentially transferred onto the rotating endless belt-shaped intermediate transfer body 70 by the primary transfer rolls 5Y, 5M, 5C, and 5K, and is combined. A colored image is formed. A recording member P such as a sheet as a transfer material accommodated in the sheet feeding cassette 20 is fed by the sheet feeding / conveying means 21, passes through a plurality of intermediate rolls 22 A, 22 B, 22 C, 22 D, and a registration roll 23, and is secondary A color image is transferred onto the recording member P at a time by being conveyed to a secondary transfer roll 5A as a transfer means. The recording member P to which the color image has been transferred is fixed by the heat roll type fixing device 24, is sandwiched by the paper discharge roll 25, and is placed on the paper discharge tray 26 outside the apparatus.

  On the other hand, after the color image is transferred to the recording member P by the secondary transfer roll 5A, the residual toner is removed from the endless belt-shaped intermediate transfer body 70 from which the recording member P is separated by the curvature by the cleaning means 6A.

  During the image forming process, the primary transfer roll 5K is always in pressure contact with the photoreceptor 1K. The other primary transfer rolls 5Y, 5M, and 5C are in pressure contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roll 5A comes into pressure contact with the endless belt-shaped intermediate transfer body 70 only when the recording member P passes through the secondary transfer roll 5A and secondary transfer is performed.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R.

  The housing 8 includes image forming units 10Y, 10M, 10C, and 10K, and an endless belt-shaped intermediate transfer body unit 7.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1K in the figure. The endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 that can be rotated by winding rolls 71, 72, 73, 74, and 76, primary transfer rolls 5Y, 5M, 5C, and 5K, and a cleaning unit. 6A.

  The image forming units 10Y, 10M, 10C, and 10K and the endless belt-shaped intermediate transfer body unit 7 are integrally pulled out from the main body A by the drawer operation of the housing 8.

  In this way, toner images are formed on the photoreceptors 1Y, 1M, 1C, and 1K by charging, exposure, and development, and the toner images of the respective colors are superimposed on the endless belt-shaped intermediate transfer body 70, and are collectively applied to the recording member P. The image is transferred and fixed by the fixing device 24 by pressing and heating. The photoreceptors 1Y, 1M, 1C, and 1K after transferring the toner image to the recording member P are cleaned with the cleaning device 6A to remove the toner remaining on the photoreceptor, and then the above-described charging, exposure, and development cycle. The next image formation is performed.

  Next, an image forming method when the toner according to the present invention is used as a non-magnetic one-component developer will be described. FIG. 2 is an example of a full-color image forming apparatus that uses a non-magnetic one-component developer. An image forming apparatus 100 shown in FIG. 2 is a typical image forming apparatus in which the above-described developing device 20 can be mounted. 2 includes a charging brush 2 for uniformly charging the surface of a photosensitive drum 1 to a predetermined potential around a rotating electrostatic latent image carrier (hereinafter also referred to as a photosensitive drum) 1, and a photosensitive member. A cleaner 6 for removing residual toner on the drum 1 is provided.

  The laser scanning optical system 3 scans and exposes the photosensitive drum 1 uniformly charged by the charging brush 2 to form an electrostatic latent image on the photosensitive drum 1. The laser scanning optical system 3 includes a laser diode, a polygon mirror, and an fθ optical element, and print data for each of yellow, magenta, cyan, and black is transferred from the host computer to the control unit. Based on the print data for each color, a laser beam is sequentially output, and the photosensitive drum 1 is scanned and exposed to form an electrostatic latent image for each color.

  The developing device unit 40 that accommodates the developing device 4 supplies toner of each color to the photosensitive drum 1 on which the electrostatic latent image is formed to perform development. The developing device unit 40 is provided with four developing devices 4Y, 4M, 4C, and 4Bk each containing non-magnetic one-component toners of yellow, magenta, cyan, and black around the support shaft 33. Rotating to the center, each developing device 4 is guided to a position facing the photosensitive drum 1.

  The developing device unit 40 rotates around the support shaft 33 each time an electrostatic latent image of each color is formed on the photosensitive drum 1 by the laser scanning optical system 3, and stores the corresponding color toner. 4 is guided to a position facing the photosensitive drum 1. Then, each of the developing devices 4Y, 4M, 4C, and 4Bk sequentially supplies each charged color toner to the photosensitive drum 1 for development.

  In the image forming apparatus of FIG. 2, an endless intermediate transfer belt 7 is provided downstream of the developing device unit 40 in the rotation direction of the photosensitive drum 1, and is driven to rotate in synchronization with the photosensitive drum 1. The intermediate transfer belt 7 comes into contact with the photosensitive drum 1 at a portion pressed by the primary transfer roller 5 and transfers a toner image formed on the photosensitive drum 1. Further, a secondary transfer roller 73 is rotatably provided so as to face the support roller 72 that supports the intermediate transfer belt 7, and on the intermediate transfer belt 7 at a portion where the support roller 72 and the secondary transfer roller 73 face each other. The toner image is pressed and transferred onto a recording material P such as recording paper.

  A cleaner 8 for removing residual toner on the intermediate transfer belt 7 is provided between the full-color developing device unit 40 and the intermediate transfer belt 7 so as to be able to contact with and separate from the intermediate transfer belt 7.

  The paper feeding means 60 that guides the recording material P to the intermediate transfer belt 7 includes a paper feeding tray 61 that houses the recording material P, and a paper feeding roller 62 that feeds the recording material P stored in the paper feeding tray 61 one by one. It is composed of a timing roller 63 for feeding the fed recording material P to the secondary transfer site.

  The recording material P to which the toner image has been pressed and transferred is conveyed to the fixing device 24 by a conveying means 66 constituted by an air suction belt or the like, and the toner image transferred by the fixing device 24 is fixed on the recording material P. After fixing, the recording material P is transported through the vertical transport path 80 and discharged onto the upper surface of the apparatus main body 100.

  The image forming apparatus shown in FIG. 2 is one in which a replaceable developing device 4 is loaded to form an image. The developing device 4 shown in FIG. 3A is usually called a toner cartridge, and stores a predetermined amount of toner inside a part where components such as a developing roller are arranged. The developing device supplied in the form of a toner cartridge is loaded at a predetermined position in the image forming apparatus, and then the developer stored therein is supplied to the photosensitive drum for development, and a predetermined number of images are formed and developed. When the agent runs out, it is removed from the apparatus and a new toner cartridge is loaded.

  FIG. 3B is a schematic diagram illustrating an example of a cross-sectional configuration of the developing device 4. Hereinafter, the developing device 4 is also referred to as a toner cartridge 4. The toner cartridge 4 has a buffer chamber 42 adjacent to the developing roller 41 and a hopper 43 adjacent to the buffer chamber 42.

  The developing roller 41 has a conductive cylindrical base and an elastic layer formed on the outer periphery of the base using a material having high hardness such as silicone rubber.

  In the buffer chamber 42, a blade 44, which is a toner regulating member, is disposed in pressure contact with the developing roller 41. The blade 44 regulates the charge amount and adhesion amount of toner on the developing roller 41. It is also possible to further provide an auxiliary blade 45 for assisting regulation of the toner charge amount and adhesion amount on the developing roller 41 on the downstream side of the blade 41 with respect to the rotation direction of the developing roller 41.

  A supply roller 46 is pressed against the developing roller 41. The supply roller 46 is driven to rotate in the same direction as the developing roller 41 (counterclockwise direction in the drawing) by a motor (not shown). The supply roller 46 has a conductive cylindrical substrate and a foam layer formed of urethane foam or the like on the outer periphery of the substrate.

  The hopper 43 contains toner T as a one-component developer. The hopper 43 is provided with a rotating body 47 for stirring the toner. A film-like conveying blade is attached to the rotating body 47, and the toner is conveyed by the rotation of the rotating body 47 in the arrow direction. The toner conveyed by the conveying blades is supplied to the buffer chamber 42 through a passage 44 provided in a partition wall that separates the hopper 43 and the buffer chamber 42. The shape of the conveying blade is bent while conveying the toner in front of the rotation direction of the blade as the rotating body 47 rotates, and returns to a straight state when the left end of the passage 48 is reached. In this way, the blades return the toner to the passage 48 by returning the shape straight after passing through the curved state.

  The passage 48 is provided with a valve 321 for closing the passage 48. This valve is a film-like member, one end of which is fixed to the upper right side surface of the passageway 48 of the partition wall. When toner is supplied from the hopper 43 to the passageway 48, the passageway 48 is opened by being pushed rightward by the pressing force from the toner. It is like that. As a result, toner is supplied into the buffer chamber 42.

  Further, a regulating member 322 is attached to the other end of the valve 321. The regulating member 322 and the supply roller 46 are arranged so as to form a slight gap even when the valve 321 closes the passage 48. The regulating member 322 adjusts so that the amount of toner accumulated at the bottom of the buffer chamber 42 does not become excessive, so that a large amount of toner collected from the developing roller 41 to the supply roller 46 does not fall to the bottom of the buffer chamber 42. Adjusted.

  In the toner cartridge 4, the developing roller 41 is rotated in the direction of the arrow during image formation, and the toner in the buffer chamber 42 is supplied onto the developing roller 41 by the rotation of the supply roller 46. The toner supplied onto the developing roller 41 is charged and thinned by a blade 44 and an auxiliary blade 45 and then transported to a region facing the image carrier to develop an electrostatic latent image on the image carrier. Provided. The toner that has not been used for development returns to the buffer chamber 42 as the developing roller 41 rotates, and is scraped and collected from the developing roller 41 by the supply roller 46.

  The toner according to the present invention does not change the crystal structure of the compound in the toner at the heating temperature during fixing in the prior art, and a toner image having stable color reproducibility can be obtained with a known fixing device. It is done. By the way, in recent years, there is a movement to reduce the energy consumption of the image forming apparatus from the viewpoint of consideration for the global environment. Of these, the reduction of energy consumption in the fixing process has attracted attention, and so-called low-temperature fixing technology for fixing a toner image at a temperature lower than the current fixing temperature has been adopted.

  That is, when the toner according to the present invention is a toner compatible with low-temperature fixing, the surface temperature of the heating member in the fixing device is preferably set to less than 140 ° C., and the surface temperature of the heating member is set to less than 130 ° C. Is more preferable.

  Under the set temperature, it is required to efficiently supply heat supplied from the heating member to the transfer sheet, and so-called belt fixing using a heat-resistant belt as either the heating member or the pressure member. The method is preferred.

  FIG. 4 shows an example of a belt fixing type fixing device (a type using a belt and a heating roller) capable of fixing the toner according to the present invention.

  The fixing device 24 shown in FIG. 4 is a type that uses a belt and a heating roller to secure a nip width, and is pressed against the fixing roller 240 via the fixing roller 240, the seamless belt 241, and the seamless belt 241. The pressure pad (pressure member) 242a, the pressure pad (pressure member) 242b, and the lubricant supply member 243 constitute main parts.

  The fixing roller 240 is formed of a heat-resistant elastic layer 240b and a release layer (heat-resistant resin layer) 240c around a metal core (cylindrical metal core) 240a, and a heat source is provided inside the core 240a. A halogen lamp 244 is arranged. The surface temperature of the fixing roller 240 is measured by the temperature sensor 245, and the halogen lamp 244 is feedback-controlled by a temperature controller (not shown) based on the measurement signal so that the surface of the fixing roller 240 is adjusted to a constant temperature. The seamless belt 241 contacts the fixing roller 240 so as to be wound at a predetermined angle, thereby forming a nip portion.

  Inside the seamless belt 241, a pressure pad 242 having a low friction layer on its surface is disposed in a state of being pressed against the fixing roller 240 via the seamless belt 241. The pressure pad 242 is provided with a pressure pad 242a to which a strong nip pressure is applied and a pressure pad 242b to which a weak nip pressure is applied, and is held by a holder 242c made of metal or the like.

  A belt traveling guide is attached to the holder 242c so that the seamless belt 241 slides and rotates smoothly. The belt running guide is preferably a member having a low coefficient of friction because it rubs against the inner surface of the seamless belt 241, and a member having low thermal conductivity is preferred so that heat cannot be taken away from the seamless belt 241. In addition, as a specific example of the material of the seamless belt 241, a polyimide is mentioned, for example.

  The toner image formed with the toner according to the present invention is finally transferred onto the transfer material P, and fixed on the transfer material by a fixing process to form an image. The transfer material P used for the image formation is a support for holding a toner image, and is usually called an image support, a recording material, or transfer paper. Specifically, various transfer materials such as plain paper and fine paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, plastic film for OHP, cloth, etc. However, it is not limited to these.

Example 1
(Preparation of toners 1 to 18)
(Production of toner 1 (toner by kneading and pulverization method))
The following toner components were 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.

100 parts by mass of polyester resin (condensation product of bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid, weight average molecular weight 20,000)
Compound examples (1-1) and (2-1) 2 parts by mass in total
However, the amount of the compound example (2-1) used is 2% by mass.
Mold release agent (pentaerythritol tetrastearate) 6 parts by weight Charge control agent (boron dibenzylate) 1 part by weight The mixture is kneaded with a twin-screw extrusion kneader, then coarsely pulverized with a hammer mill, and then a turbo mill pulverizer (turbo By pulverizing with an airflow classifier utilizing the Coanda effect, colored particles having a volume-based median diameter of 5.5 μm were obtained.

  Next, the following external additives were added to the colored particles, and external addition processing was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to prepare “Toner 1”.

Hexamethylsilazane-treated silica (average primary particle size 12 nm) 0.6 parts by mass n-octylsilane-treated titanium dioxide (average primary particle size 24 nm)
0.8 parts by mass The external addition treatment by the Henschel mixer 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.

(Preparation of Toner 2-18 (Toner by Emulsion Association Method))
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, 2 parts by mass of (1-1) and (1-2) in the compound examples are gradually added in the ratio shown in Table 1, and “Clearmix W Motion CLM-0.8 ( "Mtechnic Co., Ltd.)" was subjected to dispersion treatment to prepare "Colorant fine particle dispersion 1".

  “Colorant fine particle 1” in “Colorant fine particle dispersion 1” had a volume-based median diameter of 98 nm. The volume-based median diameter was measured using “MICROTRAC UPA-150 (manufactured by HONEYWELL)” under the following measurement conditions.

Sample refractive index 1.59
Sample specific gravity 1.05 (in terms of spherical particles)
Solvent refractive index 1.33
Solvent viscosity 0.797 (30 ° C), 1.002 (20 ° C)
0-point adjustment Ion-exchanged water was added to the measurement cell for preparation.

Production of “core part resin particles 1” “core part resin particles 1” having a multilayer structure were produced 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 shown below (Structural Formula 1) together with 3040 parts by mass of ion-exchanged water are charged 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 is added dropwise, the system is heated and stirred at 75 ° C. for 2 hours. Polymerization (first stage polymerization) was performed to prepare resin particles. This resin particle is referred to as “resin particle A1”. The “resin particle A1” produced by the first stage polymerization had a weight average molecular weight of 16,500.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was charged into a flask equipped with a stirrer, and then paraffin wax “HNP-57 (manufactured by Nippon Wax Co., Ltd.)” 93 as a release agent. .8 parts by mass was added and dissolved by heating to 90 ° C. In this way, a monomer solution was prepared.

Styrene 101.1 parts by weight n-butyl acrylate 62.2 parts by weight Methacrylic acid 12.3 parts by weight n-octyl mercaptan 1.75 parts by weight On the other hand, 3 parts by weight of the anionic surfactant is dissolved in 1560 parts by weight of ion-exchanged water. An aqueous surfactant solution was prepared and heated to 98 ° C. A mechanical system having a circulation path after adding 32.8 parts by mass (in terms of solid content) of the “resin particles A1” to the surfactant aqueous solution and further adding the monomer solution containing the paraffin wax. It was mixed and dispersed for 8 hours with a disperser “CLEAMIX (M Technique Co., Ltd.)”. 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. This resin particle is referred to as “resin particle A2”. The “resin particle A2” produced by the second stage polymerization had a weight average molecular weight of 23,000.

(C) Third-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 to the “resin particles A2” obtained by the second-stage polymerization. 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 the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). It cooled to 28 degreeC and produced "resin particle 1 for core parts." Prepared by third stage polymerization. The “core part resin particles 1” had a weight average molecular weight of 26,800.

Production of “resin particles for shell” Polymerization reaction and reaction were 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 part 1” was changed to the following: Subsequent treatment was performed to produce “shell resin particles 1”.

Styrene 624 parts by weight 2-ethylhexyl acrylate 120 parts by weight Methacrylic acid 56 parts by weight n-octyl mercaptan 16.4 parts by weight Preparation of “Toner 2” “Toner 2” was prepared by the following procedure.

(A) Formation of core part In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
Resin particle for core part 420.7 parts by mass (solid content conversion)
900 parts by mass of ion-exchanged water 200 parts by mass of the colorant particle dispersion 1 were added 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 Coulter)”. When the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was ion-exchanged. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of water.

  After termination of the association, the core temperature 1 was prepared by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.

  The average circularity of the “core part 1” was measured by “FPIA 2000 (manufactured by Systex)” and found to be 0.912.

(B) Formation of shell Next, the above-mentioned liquid is brought to 65 ° C., and 96 parts by mass of “shell resin particles 1” is added. Further, 2 parts by mass of magnesium chloride hexahydrate is added to 1000 parts by mass of ion-exchanged water. After the dissolved aqueous solution was added over 10 minutes, the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this way, after the “shell resin particles 1” were fused to the surface of the “core part 1”, an aging treatment was performed 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 colored 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. “Colored particles 2” having a shell were produced.

(C) External Addition Treatment The following external additives were added to the produced “colored particles 2” and subjected to external addition treatment with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to produce “Toner 2”.

Hexamethylsilazane-treated silica (average primary particle size 12 nm) 0.6 parts by mass n-octylsilane-treated titanium dioxide (average primary particle size 24 nm)
0.8 parts by mass The external addition treatment by the Henschel mixer 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.

Preparation of “Toners 3 to 18” “Toner 3” was prepared in the same manner as in the preparation of “Toner 2”, except that Compound Example (1-1) and Compound Example (2-1) were changed to various compounds shown in Table 1. To 18 ".

(Preparation of comparative toners 1 to 3)
Production of “Comparative Toner 1” In the production of “Toner 2”, instead of Compound Example (1-1), the compound example (2-1) was used instead of the copper phthalocyanine compound produced by the following procedure. A “Comparative Toner 1” was prepared in the same procedure except that this was not done.

(Preparation of copper phthalocyanine)
The following compounds were supplied to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a heating device, and reacted for 2 hours while maintaining at 180 to 185 ° C.

Phthalic anhydride 21.0 parts by weight Urea 23.0 parts by weight Cuprous chloride anhydrous 3.6 parts by weight Ammonium molybdate 0.007 parts by weight tert-butylxylene 100 parts by weight (mainly tert-butyl-o-xylene And a mixture containing tert-butyl-m-xylene and tert-butyl-p-xylene)
After completion of the reaction, the reaction product was cooled, and then the reaction product was collected by filtration under reduced pressure. The recovered reaction product was charged into 400 parts by mass of methanol and washed, and then filtered. This washing with methanol and filtration were performed twice.

  After removing methanol and the like from the filtrate, the reaction product was added to 4000 parts by mass of a 2% aqueous sodium hydroxide solution, subjected to boiling washing treatment for 1 hour, filtered, and further filtered and washed with water. Washing with hot water was repeated until neutralization. After carrying out washing with hot water, the reaction product was then added to 2000 parts by mass of 2% hydrochloric acid, followed by boiling washing treatment and filtration treatment as described above, and washing with hot water was repeated until the washing water was neutralized. In this way, a “copper phthalocyanine compound” was obtained.

Preparation of “Comparative Toner 2” In preparation of “Toner 2”, Compound Example (1-1) was changed to the following compound disclosed in JP-A-5-239368, and Compound Example (2-1) was prepared. “Comparative Toner 2” was prepared in the same procedure except that was not used.

Preparation of “Comparative Toner 3” “Comparative Toner 2” was prepared in the same procedure except that Compound Example (2-1) was not used in the preparation of “Toner 2”.

(Development of developer)
Preparation of “Developers 1 to 18” and “Comparative Developers 1 to 3” Each of the above “Toners 1 to 18” and “Comparative Toners 1 to 3” was coated with a silicone resin and had a volume average particle diameter of 60 μm. Ferrite carriers were mixed to prepare “Developers 1-18” and “Comparative Developers 1-3” shown in Table 1 having a toner concentration of 6%.

Evaluation Experiment Evaluation was performed using a developing device in which each developer was added to a commercially available composite printer “bizhub Pro C500 (manufactured by Konica Minolta Business Technologies, Inc.)” corresponding to the two-component development type image forming apparatus of FIG. It was loaded.

  Further, the belt fixing type fixing device shown in FIG. 4 was mounted on the printer for evaluation. Various conditions such as the surface material and surface temperature of the heating roller in the belt fixing type fixing device described above were set as follows.

Fixing speed: 230mm / sec
Heat roller surface material: Polytetrafluoroethylene (PTFE)
Heating roller surface temperature: 125 ° C
In the evaluation, the toner prepared above was loaded in the evaluation device in order, and the following items were evaluated in an environment of normal temperature and normal humidity (20 ° C., 55% RH).

  The print is performed in an environment of normal temperature and humidity (25 ° C., 55% RH), each of a halftone image having an image density of 0.4, a solid white image, a solid black image having an image density of 0.8, and a fine line image. 3000 continuous A4 size print images of / 4 equal parts were made.

<Color turbidity>
Sensory evaluation was performed on the following criteria for the solid image sample and the 10 tone scale image sample in which the image density was changed in 10 steps. Ten evaluators were recruited and the scores of all members were added to obtain an evaluation score. Therefore, the theoretical maximum score according to this evaluation is 30 points, and the minimum score (not exceeding the conventional product) is 0 points.

3 points: The solid image has a clean finish that does not feel any color turbidity, and the 10 tone scale image has a halftone tone that does not feel any roughness. 2 points: The solid image is slightly smaller than the 3 points. Although it is inferior to the above, it is a finish that does not feel color turbidity, and the 10 tone scale image is a halftone and finish that does not feel rough. 1 point: Solid image, 10 tone scale image is more advanced than 0 point image sample However, the finish is inferior to that of the two-point image. 0 point: Both the solid image and the 10-gradation scale image are equivalent to the color development of the conventional color toner, and the finish does not feel the progress.

<Light resistance evaluation>
The solid image sample was irradiated with a xenon fade meter (70,000 lux) for 10 days, and the light resistance was evaluated by the change in reflection density before and after irradiation. The image density before and after irradiation by the xenon fade meter was measured using a “color reflection densitometer X-Rite 404A (manufactured by X-Rite)”, and a density difference of 1.0 or less was accepted.

<Toner consumption>
Using each toner, 2000 A4 size monochrome images with a pixel rate of 6% were printed, and the amount of toner consumed per printed sheet was calculated from the amount of toner consumed at the time of printing. It was. A toner having a toner consumption per print of less than 16 mg / sheet was accepted.

  The results are shown in Table 1.

  As shown in Table 1, all the developers 1 to 18 using the electrostatic image developing toner according to the present invention have good results for the above evaluation items, and the effects of the present invention are exhibited. Was confirmed. On the other hand, Comparative Developers 1 to 3 using the toner for developing an electrostatic charge image outside of the present invention did not obtain the results obtained in the present invention for the above evaluation items, and the effects of the present invention were exhibited. Not confirmed.

(Charge amount change over time)
Qa was the charge amount when the developer was set and the first image was taken out, Qb was the charge amount when the million-th image was taken out, and the value of Qb / Qa was evaluated according to the following evaluation criteria. The results are shown in Table 2 below.

A: 0.9 or more and less than 1.1 ○: 0.8 or more and less than 0.9, or 1.1 or more and less than 1.2 Δ: 0.7 or more and less than 0.8, or 1.2 or more and less than 1.3 X: Less than 0.7 or 1.3 or more.

Offset resistance With respect to offset resistance, after fixing and fixing 10,000 sheets of A4 copy paper with a 5 mm wide solid belt image in the vertical direction with respect to the transport direction, the width is 20 mm perpendicular to the transport direction. The A4 image having the halftone image is conveyed continuously in the horizontal direction by 10,000 sheets, and is temporarily stopped. After the machine was stopped overnight, the machine was started up again, and the presence or absence of image contamination due to the fixing offset phenomenon occurring on the first sheet was visually evaluated according to the following evaluation criteria. The results are shown in Table 2 below.

◎: No stain on image ○: Very slight stain on image (no problem in practical use)
X: There is a stain on the image and it is not suitable for practical use.

  According to the developer of the present invention, excellent chargeability and offset resistance can be obtained, and an image with high image quality can be reliably formed.

1 is a schematic diagram illustrating an example of a tandem full-color image forming apparatus capable of two-component development type image formation. 1 is a schematic view of a 4-cycle full-color image forming apparatus capable of image formation by a non-magnetic one-component development system. FIG. 2 is a schematic diagram illustrating an example of a developing device (toner cartridge). FIG. 3 is a schematic diagram illustrating an example of a belt fixing type fixing device using a belt and a heating roller.

Explanation of symbols

1 Photoconductor (Photoconductor drum)
4 Development device (toner cartridge)
6 Cleaning Device 7 Intermediate Transfer Belt 10 Image Forming Unit 24 Fixing Device 240 Heating Roller 241 Pressure Belt (Seamless Belt)
P Transfer material (recording material)

Claims (5)

An electrostatic charge image developing toner comprising at least a binder resin and a colorant, wherein the colorant is represented by the following general formulas (1) and (2): An electrostatic charge image developing toner comprising phthalocyanine.

(In the formula, A ₁₁ , A ₁₂ , A ₁₃ and A ₁₄ represent a benzene ring or a naphthalene ring. R ₁ , R ₂ , R ₃ , R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each independently a substituent. Represents.)

(In the formula, A ₂₁ , A ₂₂ , A ₂₃ and A ₂₄ represent a benzene ring or a naphthalene ring. R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ each independently represent a substituent.) The content of the compound represented by the general formula (2) is 0.1 to 10.0% by mass in the total amount of the compound of the general formula (1) and the compound of the general formula (2). The toner for developing an electrostatic charge image according to claim 1. R ₁ , R ₂ , R ₃ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ in the general formula (1) and R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ in the general formula (2) are halogens. Atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, quaternized heterocyclic groups containing nitrogen atoms, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, carboxy groups or the like Salt, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, Carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, amino group, acyl group Mino group, sulfonamide group, ureido group, thioureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, sulfonylureido group, acylureido group , Acylsulfamoylamino group, nitro group, mercapto group, thio group, sulfonyl group, sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, acylsulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoric acid amide 3. The electrostatic image developing toner according to claim 1, wherein the toner is one selected from a group having a phosphate ester structure, a silyloxy group, and a silyl group. 4. The electrostatic charge image developing according to claim ₁ , wherein R ₁ , R ₂ and R ₃ in the general formula (1) are alkyl groups having 1 to 4 carbon atoms. 5. toner. A developer comprising the electrostatic image developing toner according to claim 1.

Images