JP2006003499A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner capable of maintaining good image quality over a long period without damaging fogging, image density, a transfer performance and a cleaning performance by remarkably improving the dispersion state of carbon black in a toner particle. <P>SOLUTION: The toner comprises at least binding resin, the carbon black, wax components, metal phthalocyanine and/or metal phthalocyanine derivative. The toner contains polymer containing a prescribed polymerrizable monomer having an amide group as a constitutional unit, and the toluene extraction of the carbon black is ≤0.2 mass%, the dissolution of the metal phthalocyanine and/or the metal phthalocyanine derivative to styrene at 25°C is ≥3 mass%, the average roundness of the toner is 0.950 to 0.995, and the dielectric loss tangent tanδ measured at frequency of 100kHz is 0.002 to 0.015. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method, or the like. More specifically, the present invention relates to a toner used in an image forming apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like.

  Conventionally, in electrophotography, an electric latent image is formed on a photoreceptor by various means, and then the latent image is developed with toner, and the toner image is transferred to a transfer material such as paper as necessary. Thereafter, fixing is performed by heating, pressurization, heat pressurization, or solvent vapor to obtain a fixed image (for example, see Non-Patent Document 1).

  A dry toner (hereinafter referred to as “toner”) used in electrophotography is generally colored fine resin particles mainly containing a binder resin, a colorant, and waxes. Is a number average particle diameter of about 6 to 15 μm. As a method for producing a toner composed of such colored resin fine particles, a binder resin, a colorant such as a dye / pigment and / or a magnetic material, waxes and the like are melt-kneaded, the kneaded product is cooled, pulverized, and further pulverized. The so-called “pulverization method” is generally used to classify the product to obtain toner particles. However, in the pulverization method as described above, the fine particle formation and shape control of the toner particles not only lead to a decrease in productivity, but there is a limit to actively designing the internal structure of the toner particles. On the other hand, in order to overcome the problems of toner production by the pulverization method and to achieve the performance improvement by enhancing the function of the toner, toner production by the “polymerization method” is being carried out. It is roughly divided into a polymerization method and an emulsion polymerization aggregation method.

  In recent years, the field of application of image forming apparatuses using electrophotography as described above is not only a copying machine for copying original documents, but also a printer as a computer output device, or a personal copy for individuals. Furthermore, it is rapidly developing into plain paper fax machines, and various demands are increasing. In addition, copying machines are becoming more sophisticated due to digitalization. In particular, the size, speed, and color of the image forming apparatus are remarkably increased, and there is a strong demand for high reliability and high resolution. For example, the resolution that was initially 200 to 300 dpi (dot per inch) is becoming 400 to 1200 dpi, and further to 2400 dpi. In full-color image formation, the electrostatic latent image is generally developed and transferred with magenta toner, cyan toner, yellow toner, and black toner, and the toner images of each color are superimposed and fixed. Multicolor images are reproduced. In such a high-resolution and / or full-color image forming apparatus, in order to satisfy the above-described requirements, a member having high functionality in various points is used and designed with simpler components. It has become to. As a result, the functions required of the toner are further advanced, and if the toner performance cannot be improved, a more excellent image forming apparatus cannot be realized.

  For example, in recent years, in the process of developing an electrostatic latent image on a photoreceptor, the surface of the photoreceptor and the toner layer on the toner carrier are brought into contact with each other, and the surface of the photoreceptor and the surface of the toner carrier are moved relative to each other. 2. Description of the Related Art Contact developing devices that employ a one-component contact developing method that can achieve development of an electrostatic latent image have been widely used mainly in color machines. In addition, a transfer device for electrostatically transferring a toner image on an electrostatic latent image carrier or an intermediate transfer member onto a transfer material is externally used from the viewpoint of miniaturization of an image forming apparatus and prevention of ozone generation. Increasing use of a contact transfer device for performing contact transfer, in which a roller-like transfer member to which a voltage is applied is in contact with an electrostatic latent image carrier or an intermediate transfer member via the transfer material, is increasing. Yes.

  For such contact developing devices and contact transfer devices, it is effective to increase the developability and transferability, and further to the resistance to mechanical stress from these devices by making the toner particle shape spherical. On the other hand, since the specific surface area and volume of the toner particles are reduced, the dispersibility of the colorant inside the toner particles has a greater effect than expected on the developability, transferability, and matching with the image forming apparatus. .

  Among the colorants, carbon black is particularly inexpensive and is effective as a colorant for black toner. However, carbon black tends to be present inside the toner particles in an agglomerated manner, or even in the vicinity of the toner surface even when no aggregation occurs. Such a phenomenon tends to occur in black toner using carbon black in which carbon black has a fine primary particle size and is extremely difficult to uniformly disperse in toner particles compared to other colorants. This is particularly noticeable with toners produced by polymerization.

  In addition, since carbon black generally has electrical conductivity, if it is unevenly distributed in the vicinity of the toner surface, printing over a long period of time not only causes problems such as fogging due to poor charging of the toner and a decrease in image density, There is also concern about the effect on transferability.

  Conventionally, various techniques have been disclosed for improving the dispersibility of carbon black in toner particles.

  For example, by using a combination of fine particle size carbon black and a specific azo-based metal compound in the presence of a wax component, the cohesiveness of carbon black in the toner particles and the release from the toner particles can be improved and produced by a polymerization method. It is known that it can be applied to the toner used. (For example, refer to Patent Document 1).

  However, since the specific azo metal compound used in the toner generally has a pigment-like property, in order to act as a dispersant, a high shear force is applied under specific conditions. It was necessary to apply. Accordingly, the dispersibility is limited, and there is still room for improvement with respect to the charging characteristics of the toner.

  Also known is a method of producing a toner having a fine particle diameter by suspension polymerization using Ti phthalocyanine or soluble Cu phthalocyanine as a carbon black dispersion aid (see, for example, Patent Document 2).

  Although these toners have improved coloring power and chargeability to some extent, development characteristics and transferability are not considered at all. In addition, as a result of our investigation, the dispersibility of carbon black and polymerizable monomer compositions is controlled by the functional group directly bonded to the phthalocyanine ring, so that the dispersion stability is not sufficient. When the toner is produced by the polymerization method, it has been found that, due to the polymerization reaction of the polymerizable monomer, reaggregation of carbon black, a phenomenon of migration to the toner particle surface, and the like are caused.

  On the other hand, a technique is also known in which a charge control resin having a sulfonic acid group-containing acrylamide monomer as a constituent component is applied to a polymerization toner (for example, see Patent Document 3).

  Although these toners can form full-color images exhibiting good coloring power, we have found that there is room for improvement in the dispersion state of the colorant in the toner particles. It was. That is, since the improvement of the dispersibility of the colorant is attempted only with the charge control resin, the dispersion stability is not sufficient. For this reason, the colorant that has been well dispersed in the preparation stage of the polymerizable monomer composition has caused re-aggregation, a phenomenon of transfer to the toner particle surface, and the like accompanying the polymerization reaction of the polymerizable monomer. The toner as described above has not improved the matching with the image forming apparatus such as the cleaning property in the cleaning process for cleaning the transfer residue on the drum.

  That is, as described above, regarding the system design of the image forming apparatus using the contact developing unit and the contact transfer unit, there is not yet sufficient comprehensive correspondence including the carbon black used for the toner.

JP 2000-352844 A JP-A-5-70511 Japanese Patent Laid-Open No. 11-3427208 Electrophotographic Society, “Basics and Applications of Electrophotographic Technology”, Corona Co., Ltd., June 15, 1988, p46-79

  An object of the present invention is to provide a toner in which the dispersion state of carbon black in toner particles is remarkably improved.

  Another object of the present invention is to provide a toner that can maintain good image quality over a long period of time without impairing fogging, image density, transferability, and cleaning properties.

The present invention provides a toner having at least a binder resin, carbon black, a wax component, a metal phthalocyanine and / or a metal phthalocyanine derivative.
A polymer containing 0.5 to 20% by mass of a polymerizable monomer represented by the following structural formula (1) and / or (2) as a constituent unit, or a polymerizability represented by the following structural formula (3) Containing a polymer containing 0.5 to 20% by mass of a monomer and a carboxyl group-containing vinyl monomer each as a constituent unit;
The toluene extraction amount of the carbon black is 0.2% by mass or less,
The solubility in styrene at 25 ° C. of the metal phthalocyanine and / or metal phthalocyanine derivative is 3% by mass or more,
The toner has an average circularity of 0.950 to 0.995, and a dielectric loss tangent tan δ measured at a frequency of 100 kHz is 0.002 to 0.015.

（上記構造式（１）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₂とＲ₃は、それぞれ水素原子、Ｃ₁〜Ｃ₁₀のアルキル基、アルケニル基、アリール基、又はアルコキシ基、Ｘ₁は水素原子、アルカリ金属、アルカリ土類金属、又は４級アンモニウム塩を示し、ｎは１〜１０の整数を示す。）

(In the structural formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. X ₁ represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium salt, and n represents an integer of 1 to 10.)

（上記構造式（２）中、Ｒ₄は水素原子、又はメチル基を示し、Ｒ₅〜Ｒ₈は、それぞれ水素原子、Ｃ₁〜Ｃ₁₀のアルキル基、アルケニル基、アリール基、アルコキシ基、又は芳香族基を示すが、少なくとも１つは無置換又は置換基を有する芳香族基を示す。Ｘ₂は水素原子、アルカリ金属、アルカリ土類金属、又は４級アンモニウム塩を示し、ｎは１〜１０の整数を示す。）

(In the structural formula (2), R ₄ represents a hydrogen atom or a methyl group, and R _{5 to} R ₈ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, an alkoxy group, respectively. Or an aromatic group, at least one of which represents an unsubstituted or substituted aromatic group, X ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium salt; Represents an integer of -10.)

（上記構造式（３）中、Ｒ₉は水素原子、又はメチル基を示し、Ｒ₁₀とＲ₁₁は、それぞれ水素原子、Ｃ₁〜Ｃ₂₀のアルキル基、アルケニル基、アリール基、又はアルコキシ基を示す。尚、Ｒ₁₀とＲ₁₁は化学的に結合して、炭素原子以外の異種原子を有するＣ₄〜Ｃ₂₀の環状構造を形成する非芳香族有機基としても良い。）

(In the structural formula (3), R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, a C ₁ -C ₂₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. R ₁₀ and R ₁₁ may be chemically bonded to form a non-aromatic organic group that forms a C _{4 to} C ₂₀ cyclic structure having a hetero atom other than a carbon atom.

  According to the present invention, carbon contained in toner particles can be obtained by using a toner containing a specific metal phthalocyanine, a polymerizable monomer having an amide group, and carbon black and having a specific dielectric loss tangent characteristic. A toner in which the black dispersion state is remarkably improved can be obtained. As a result, it is possible to have unprecedented high coloring power and to improve the charging characteristics such as fog and transferability.

  As a result of intensive studies, the present inventors use a toner having specific metal phthalocyanines, a specific polymerizable monomer having an amide group, and carbon black in the toner particles, and having specific dielectric loss tangent characteristics. As a result, it was found that the dispersion state of carbon black in the toner particles was remarkably improved, and the present invention was completed.

  First, the structural features and raw materials used of the toner of the present invention will be described.

  The toner of the present invention includes at least a metal phthalocyanine and / or a binder resin, carbon black, and a central metal selected from the group consisting of [Cr, Fe, Co, Ni, Zn, Mn, Mg, Al]. A polymer containing 0.5 to 20% by mass of a metal phthalocyanine derivative and a polymerizable monomer represented by the following structural formula (1) and / or (2) as a constituent unit, or the following structural formula (3) It contains a polymer containing 0.5 to 20% by mass of each of the represented polymerizable monomer and carboxyl group-containing vinyl monomer as constituent units.

［構造式（１）において、Ｒ₁は水素原子又はメチル基を示す。Ｒ₂及びＲ₃はそれぞれ独立して水素原子、アリール基又はＣ₁〜Ｃ₁₀のアルキル基、アルケニル基若しくはアルコキシ基を示し、Ｘ₁は水素原子、アルカリ金属原子、アルカリ土類金属原子又は４級アンモニウム塩を示し、ｎは１〜１０の整数を示す。］

[In Structural Formula (1), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an aryl group, or a C _{1 to} C ₁₀ alkyl group, alkenyl group or alkoxy group, and X ₁ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or 4 Represents a quaternary ammonium salt, and n represents an integer of 1 to 10. ]

［構造式（２）において、Ｒ₄は水素原子又はメチル基を示す。Ｒ₅〜Ｒ₈はそれぞれ独立して水素原子、アリール基、芳香族基又はＣ₁〜Ｃ₁₀のアルキル基、アルケニル基若しくはアルコキシ基を示すが、Ｒ₅〜Ｒ₈のうち少なくとも１つは無置換又は置換基を有する芳香族基を示す。Ｘ₂は水素原子、アルカリ金属原子、アルカリ土類金属原子又は４級アンモニウム塩を示す。］

[In Structural Formula (2), R ₄ represents a hydrogen atom or a methyl group. R _{5 to} R ₈ each independently represents a hydrogen atom, an aryl group, an aromatic group, or a C _{1 to} C ₁₀ alkyl group, alkenyl group or alkoxy group, but at least one of R _{5 to} R ₈ is absent. An aromatic group having a substituent or a substituent is shown. X ₂ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a quaternary ammonium salt. ]

［構造式（３）において、Ｒ₉は水素原子又はメチル基を示し、Ｒ₁₀及びＲ₁₁はそれぞれ独立して水素原子、アリール基又はＣ₁〜Ｃ₂₀のアルキル基、アルケニル基若しくはアルコキシ基を示す。なお、Ｒ₁₀とＲ₁₁は相互に連結して、炭素原子以外の異種原子を有し且つＣ₄〜Ｃ₂₀の環状構造を有する非芳香族有機基を形成してもよい。］

[In Structural Formula (3), R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ each independently represents a hydrogen atom, an aryl group, or a C _{1 to} C ₂₀ alkyl group, alkenyl group, or alkoxy group. Show. R ₁₀ and R ₁₁ may be connected to each other to form a non-aromatic organic group having a hetero atom other than a carbon atom and having a C _{4 to} C ₂₀ cyclic structure. ]

  By configuring the toner as described above, it is possible to remarkably improve the dispersion state of carbon black in the toner particles and to impart desirable characteristics to the toner.

  The toner of the present invention is a fine coloring containing a polymer containing at least a binder resin, carbon black, a metal phthalocyanine and / or a metal phthalocyanine derivative, and a specific polymerizable monomer having an amide group as constituent units. The toner particles are composed of particles, and various additives may be mixed and added to the toner particles as necessary.

  In the present invention, toner particles are produced by allowing the specific metal phthalocyanine and / or metal phthalocyanine derivative as described above to coexist in the toner and a polymer containing a specific polymerizable monomer having an amide group as a constituent unit. The dispersion state of carbon black in the inside is remarkably improved. Regarding this reason, the present inventors consider as follows.

  That is, a metal phthalocyanine and / or a metal phthalocyanine derivative (hereinafter referred to as “a metal phthalocyanine and / or a metal phthalocyanine derivative” selected from the group consisting of [Cr, Fe, Co, Ni, Zn, Mn, Mg, Al] used in the present invention. The “metal phthalocyanines”) can have a five-coordinate structure or a six-coordinate structure capable of coordinating a ligand in the axial direction with respect to a phthalocyanine ring which is a macrocyclic compound.

  On the other hand, a polymer containing a specific polymerizable monomer having an amide group used in the present invention as a constituent unit, that is, a polymerizable monomer represented by at least the structural formula (1) and / or (2). 0.5-20% by mass of a polymer containing 0.5-20% by mass as a constituent unit, or a polymerizable monomer represented by the structural formula (3) and a carboxyl group-containing vinyl monomer, respectively. Since a polymer (hereinafter referred to as “polymer ligand”) containing% as a constituent unit has an unshared electron pair, it acts as a polymer ligand for the phthalocyanine ring. Therefore, a polymer complex can be formed by making both coexist.

  The polymer complex obtained by coordination of the polymer ligand to the metal phthalocyanines used in the present invention has a good affinity for the phthalocyanine ring portion with carbon black, and the polymer portion has a binder resin or other components. In addition to exhibiting an affinity with the toner constituent material, reaggregation is also prevented by steric hindrance, so that a good dispersion state can be produced.

  The metal phthalocyanines used in the present invention have a divalent metal, a trivalent or tetravalent substituted metal, or an oxy metal as a central metal because it needs to be a pentacoordinate structure or a hexacoordinate structure. Specifically, it is any one selected from the group consisting of [Cr, Fe, Co, Ni, Zn, Mn, Mg, Al]. The central metal of the metal phthalocyanines is preferably one selected from the group consisting of [Cr, Fe, Co, Zn, Mn] in consideration of easy incorporation of the axial ligand. Zn phthalocyanine (zinc phthalocyanine) having a central metal of Zn represented by the following structural formula (4) capable of taking a coordinate structure is particularly preferably selected. The polymer complex constituted by the polymer used in the present invention and the following structural formula (4) has particularly good adsorption characteristics with the carbon black used in the present invention, and the dispersibility of the carbon black in the toner is improved. Can be good.

  The metal phthalocyanines used in the present invention must have a solubility in styrene at 25 ° C. of 3% by mass or more, preferably 5% by mass or more. In order to improve the dispersibility of carbon black, unless the metal phthalocyanines are dissolved in the binder resin at the molecular level, the effect as a dispersant cannot be fully exhibited.

  Known metal phthalocyanines used in the present invention can be used. That is, it is not particularly limited as long as it has a phthalocyanine skeleton. For example, four isoindole moieties into which substituents such as carboxylic acid and sulfonic acid are introduced, aromatics, aliphatics, ethers, alcohols Those introduced with a substituent such as. However, it is not preferable that itself affects the adsorptivity of the phthalocyanine ring and the colorant and the ease of incorporation of the axial ligand.

  In the present invention, the metal phthalocyanines form a polymer complex using a polymer containing a specific polymerizable monomer having an amide group, which will be described later, as a constituent unit as a polymer ligand, and a dispersant for the colorant Therefore, the object is achieved with a very small addition amount, which is in a range where the effect of the coloring power of the metal phthalocyanines themselves can be ignored. The specific addition amount depends on the type and addition amount of carbon black used at the same time, but is 0.01 to 0.5 parts by mass, preferably 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the binder resin. Part by mass.

  On the other hand, the polymer containing a specific polymerizable monomer component having an amide group used as a polymer ligand as a constituent unit with respect to the metal phthalocyanines used in the present invention is at least the structural formula (1) or A polymer containing 0.5 to 20% by mass of a polymerizable monomer represented by (2) as a constituent unit, or a polymerizable monomer represented by the structural formula (3) and a carboxyl group-containing vinyl monomer It is a polymer containing 0.5 to 20% by mass of each as a constituent unit.

  Since the polymer used as such a polymer ligand has at least a lone pair in the molecular structure of the polymerizable monomer represented by the structural formulas (1) to (3), It can act as a polymer ligand for the metal phthalocyanines, and forms a polymer complex with the metal phthalocyanines.

  In addition, since the polymers as the polymer ligands used in the present invention all have negative charge control ability, not only the dispersibility of carbon black in the toner particles is preferably improved, but also the carbon black From the viewpoint of both dispersibility and chargeability, it is possible to develop favorable characteristics for the negatively chargeable toner.

In the structural formula (1), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an aryl group, or a C _{1 to} C ₁₀ alkyl group, alkenyl group or alkoxy group, and X ₁ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or 4 Represents a quaternary ammonium salt, and n represents an integer of 1 to 10.

Specific examples of the polymerizable monomer represented by the structural formula (1) include 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-n-butanesulfonic acid, 2 -Acrylamide-n-hexanesulfonic acid, 2- (meth) acrylamide-n-octanesulfonic acid, 2- (meth) acrylamide-n-dodecanesulfonic acid, 2- (meth) acrylamide-n-tetradecanesulfonic acid, 2- (Meth) acrylamide-2,2,4-trimethylpentanesulfonic acid, or an alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, or the like thereof. Of these, 2-acrylamido-2-methylpropanesulfonic acid (in the above structural formula (1), R ₁ is a hydrogen atom, R ₂ and R ₃ are methyl groups, X ₁ is a hydrogen atom, and n is 1) And the like are preferably used.

In the structural formula (2), R ₄ represents a hydrogen atom or a methyl group. R _{5 to} R ₈ each independently represents a hydrogen atom, an aryl group, an aromatic group, or a C _{1 to} C ₁₀ alkyl group, alkenyl group or alkoxy group, but at least one of R _{5 to} R ₈ is absent. An aromatic group having a substituent or a substituent is shown. X ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal or a quaternary ammonium salt. Specific examples of the polymerizable monomer represented by the structural formula (2) include 2-acrylamido-1-phenylethanesulfonic acid, 2-acrylamido-2-phenylethanesulfonic acid, and 2-acrylamido-1-. (4-Methylphenyl) ethanesulfonic acid, 2-acrylamide-2- (4-methylphenyl) ethanesulfonic acid, 2-acrylamido-1-methyl-1-phenylethanesulfonic acid, 2-acrylamido-2-methyl-2 -Phenylethanesulfonic acid, 2-acrylamido-1- (4-tert-butylphenyl) ethanesulfonic acid, 2-acrylamido-2- (4-tert-butylphenyl) ethanesulfonic acid, 2-acrylamido-1- (4 -Chlorophenyl) ethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) Ethanesulfonic acid, or their alkali metal salts, alkaline earth metal salts, quaternary ammonium salts and the like. Among these, 2-acrylamido-2- (4-methylphenyl) ethanesulfonic acid (in the above structural formula (2), R ₄ is a hydrogen atom, R ₅ is a hydrogen atom, R ₆ is a 4-methylphenyl group, R ₇ is preferably a hydrogen atom, R ₈ is a hydrogen atom, and X ₂ is a hydrogen atom).

Furthermore, in the structural formula (3), R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an aryl group, or a C _{1 to} C ₂₀ alkyl group, alkenyl group or alkoxy group. Indicates a group. R ₁₀ and R ₁₁ may be connected to each other to form a non-aromatic organic group having a hetero atom other than a carbon atom and having a C _{4 to} C ₂₀ cyclic structure.

Specific examples of the polymerizable monomer represented by the structural formula (3) include (meth) acrylamide; N-butoxymethyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide, N-methyl ( N-substituted (meth) acrylamides such as meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide; N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) And (meth) acrylamide containing a cyclic structure such as acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloyl-4-piperidone, and the like. Among these, N-butoxymethylacrylamide (corresponding to the case where R ₉ is a hydrogen atom, R ₁₀ is a butoxy group, and R ₁₁ is a methyl group in the above structural formula (3)) is preferably used.

  Examples of the carboxyl group-containing vinyl monomer used in combination with the polymerizable monomer represented by the structural formula (3) include maleic acid, a half-esterified product of maleic acid, fumaric acid, and a half-ester of fumaric acid. Dispersed state in the binder resin of hydride, itaconic acid, half-esterified product of itaconic acid, crotonic acid, cinnamic acid and carboxyl group-containing vinyl monomer represented by the following structural formula (5) or (6) Is preferable because it is easy to adjust.

［構造式（５）中、Ｒ₁₂は水素原子又はメチル基を示し、Ｒ₁₃はＣ₂〜Ｃ₆のアルキレン基を示し、Ｘ₃は水素原子、アルカリ金属原子、アルカリ土類金属原子又は４級アンモニウム塩を示し、ｍは０〜１０の整数を示す。］

[In the structural formula (5), R ₁₂ represents a hydrogen atom or a methyl group, R ₁₃ represents a C _{2 to} C ₆ alkylene group, and X ₃ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or 4 Represents a quaternary ammonium salt, and m represents an integer of 0 to 10. ]

［構造式（６）中、Ｒ₁₄は水素原子又はメチル基を示し、Ｒ₁₅はＣ₂〜Ｃ₄のアルキレン基を示し、Ｒ₁₆はエチレン基、ビニレン基又は１，２−シクロへキシレン基を示し、Ｘ₄は水素原子、アルカリ金属原子、アルカリ土類金属原子又は４級アンモニウム塩を示す。］

[In the structural formula (6), R ₁₄ represents a hydrogen atom or a methyl group, R ₁₅ represents a C _{2 to} C ₄ alkylene group, and R ₁₆ represents an ethylene group, a vinylene group or a 1,2-cyclohexylene group. X ₄ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a quaternary ammonium salt. ]

  Examples of the polymerizable monomer represented by the general formula (5) include (meth) acrylic acid, (meth) acrylic acid dimer, ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. Examples of the polymerizable monomer represented by the general formula (6) include monohydroxyethyl (meth) acrylate succinate, monohydroxyethyl (meth) acrylate maleate, monohydroxyethyl (meth) acrylate fumarate, Examples thereof include monohydroxyethyl (meth) acrylate phthalate and 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate. Of these, (meth) acrylic acid, succinic acid monohydroxyethyl (meth) acrylate, and the like are more preferable.

  In the present invention, as a polymer to be a polymer ligand, a polymer containing at least a polymerizable monomer represented by the structural formula (1) as a constituent unit (hereinafter referred to as “R-1 type polymer”). ), Or a polymer containing at least a polymerizable monomer represented by the structural formula (2) as a constituent unit (hereinafter referred to as “R-2 type polymer”), the structural formula (1) or ( The content of the polymerizable monomer represented by 2) in the R-1 type polymer or R-2 type polymer is 0.5 to 20% by mass (based on the mass of the monomer used). Contain. In the present invention, the polymerizable monomer represented by the structural formula (1) or (2) is used as a constituent unit in the R-1 type polymer or R-2 type polymer in an amount of 0.5 to 20% by mass. The inclusion includes, for example, containing only 0.5 to 20% by mass of one of the polymerizable monomers represented by the structural formula (1) or (2) in the R-1 type polymer. Also contains both the polymerizable monomer represented by Structural Formula (1) and the polymerizable monomer represented by Structural Formula (2), and the total content of these polymerizable monomers is You may make it be 0.5-20 mass%.

  Moreover, the polymer (henceforth "R-3" which contains the polymeric monomer represented by Structural formula (3) and a carboxyl group-containing vinyl-type monomer as a structural unit as a polymer which is a polymer ligand. In the case of using a "type polymer"), the content of the polymerizable monomer represented by the structural formula (3) in the R-3 type polymer is 0.5 to 20% by mass (of the monomer used). (Mass basis).

  The content of the polymer monomer represented by the structural formula (1) or (2) in the R-1 type polymer or the R-2 type polymer, or the structural formula (3) in the R-3 type polymer. When the content of the represented polymerizable monomer is less than 0.5% by mass, the ability as a polymer ligand is not exhibited, so that the effect of dispersing carbon black cannot be obtained. On the other hand, when it exceeds 20% by mass, the chargeability of the toner is adversely affected. In particular, there is a problem with environmental stability. Further, when manufacturing toner particles by a polymerization method, it is difficult to control the shape of the toner particles.

  Further, in the polymer (polymer B) having a polymerizable monomer represented by the structural formula (3) and a carboxyl group-containing vinyl monomer as constituent units, a carboxyl group-containing vinyl monomer The content of is 0.5 to 20%. The polymer B is preferably obtained by copolymerizing the polymerizable monomer represented by the structural formula (3) and the carboxyl group-containing vinyl monomer at a mass ratio of 1: 5 to 3: 1. . When the content ratio of the polymerizable monomer represented by the structural formula (3) in the R-3 type polymer decreases, the ability of the polymer as a polymer ligand decreases, and the carboxyl group-containing vinyl monomer If the content ratio of the body is reduced, the chargeability becomes unstable, which is not preferable.

  The polymer as the polymer ligand as described above may be a combination of two or more polymerizable monomers represented by the above structural formulas (1) and (2), or R-1 type. It may be a mixture of a polymer and an R-2 type polymer.

  The polymer as a polymer ligand used in the present invention is preferably an oligomer or polymer having a number average molecular weight (Mn) of 500 to 50,000 and a Tg of 50 to 100 ° C. It is preferable that it is soluble from the viewpoint of dispersibility in the binder resin, chargeability, and matching with the image forming apparatus.

  The polymerizable monomer represented by the structural formulas (1) to (3) is not particularly limited as long as it is a copolymerizable monomer. However, in order to increase the affinity with the binder resin, a polymerizable vinyl is used. Monomers are preferred, and in particular, those similar to the binder resin described below and the polymerizable monomer constituting the binder resin used in the method of directly obtaining toner particles by a polymerization method are preferably used. At this time, a small amount of a crosslinking agent may be added as long as the dispersibility of the carbon black is not hindered.

  The production method of the polymer used in the present invention can be produced by a conventionally known production method.

  The carbon black of the present invention must have a toluene extraction amount of 0.2% by mass or less. When the amount of toluene extracted exceeds 0.2% by mass, the charging characteristics of the toner are reduced due to the interaction between the metal phthalocyanines used in the present invention and the toluene extract. This tends to exacerbate fog.

  Further, the pH of the carbon black of the present invention is preferably 5.5 to 10.5. When the pH of the carbon black is less than 5.5, the dispersibility of the carbon black is inferior and the coloring power of the toner is inferior. On the other hand, if the pH exceeds 10.5, transferability deteriorates due to poor charging due to carbon black.

  Further, the DBP oil absorption of the carbon black of the present invention is preferably 20 to 150 ml / 100 g. When the DBP oil absorption is less than 20 ml / 100 g, carbon black exists in the toner particles as primary particles, and although there is no problem with coloring power, there is a tendency to be unevenly distributed in the vicinity of the toner surface and the transferability tends to deteriorate. It can be seen. On the other hand, when the amount exceeds 100 ml / 100 g, transferability deteriorates due to poor charging due to carbon black.

  In the present invention, in order to achieve both high image density and toner charging stability, the carbon black content with respect to the toner particles is preferably 0.8 to 20% by mass, more preferably 2 to 2%. 15% by mass.

  When the carbon black content is less than 0.8% by mass, the coloring power as a toner is low, and it is difficult to achieve a high image density. When it exceeds 20% by mass, even when used in combination with the alkali metal element of the present invention, a specific organometallic compound, or even a polyester resin, it becomes difficult to uniformly disperse carbon black, and the toner has sufficient conductivity. Therefore, the object of the present invention cannot be achieved satisfactorily.

  Next, various measurement methods according to the present invention will be described.

(1) Measurement of toluene extraction amount of carbon black Measured according to DIN 53553.

(2) Measurement of DBP oil absorption of carbon black Measured according to DIN 53601.

(3) Measurement of pH of carbon black Measured according to DIN ISO 787/9.

  As an index indicating the degree of dispersibility of carbon black, as shown on page 241 of “Characteristics of Carbon Black and Optimum Formulation and Utilization Technology (issued by Technical Information Association)”, dielectric loss factor ε ″ and dielectric constant ε ′ There is a loss tangent tan δ expressed as a ratio, and the smaller this value, the better the dispersibility of the carbon black.

  In the toner of the present invention, it is essential that tan δ at a frequency of 100 kHz is in the range of 0.002 to 0.015, and more preferably 0.002 to 0.008. In the toner of the present invention, when tan δ exceeds 0.008, when printing is carried out over a long period of time, deterioration of fog, reduction of image density, and deterioration of transferability are observed. On the other hand, when tan δ is less than 0.002, the toner tends to have an excessively high charge amount (charge up), and the development characteristics deteriorate.

(4) Measuring method of dielectric loss tangent of toner Using a 4284A Precision LCR meter (manufactured by Hewlett Packard), after calibrating at a frequency of 1 KHz and 1 MHz, a dielectric loss tangent (tan δ) is calculated from a measured value of dielectric constant at a frequency of 100 kHz. To do.

Toner 0.5 is weighed, and a sample is measured by molding it into a disk shape with a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm) over a period of 2 minutes under a load of 34300 kPa (350 kgf / cm ² ). And This measurement sample is mounted and fixed on an ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm. Thereafter, an average value is calculated by measuring three times in a frequency range of 100 to 10 ⁶ Hz with a load of 3.43 N (350 g) applied.

  Specific examples of the binder resin contained in the toner of the present invention include styrene- (meth) acrylic copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming a binder resin is used. Specifically, styrene; styrene monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, ( Meth) propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylamide Is preferably used. These monomers are used alone or generally so that the theoretical glass transition temperature (Tg) described in Polymer Handbook 2nd edition III-P139-192 (manufactured by John Wiley & Sons) is 40-75 ° C. It is used by mixing appropriately. When the theoretical glass transition temperature (Tg) is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, while when it exceeds 75 ° C., the fixing point of the toner is increased.

  Furthermore, in the present invention, it is preferable to use a crosslinking agent during the synthesis of the binder resin in order to increase the mechanical strength of the toner particles.

  Among the crosslinking agents used in the toner of the present invention, difunctional linking agents such as divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 , # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Honkakusuri), and those obtained by changing the methacrylates of the above diacrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, polyethoxy Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

  These crosslinking agents are 0.01-10 mass parts with respect to 100 mass parts of polymerizable monomers which comprise binder resin, Preferably it is 0.1-5 mass parts.

  In the present invention, a resin having polarity (hereinafter referred to as “polar resin”) such as a polyester resin and a polycarbonate resin can be used in combination with the above-described binder resin. By adding a polar resin to the toner, it is desirable to expose the colorant to the surface of the toner particle, which often occurs when the colorant is present in the toner, especially when the dispersibility of the colorant in the toner particle is increased. It becomes easy to control the state.

  For example, when a toner is directly produced by a suspension polymerization method, which will be described later, a polymerizable monomer composition that becomes toner particles when a polar resin as described above is added during the polymerization reaction from the dispersion step to the polymerization step. Depending on the balance of polarity exhibited by the aqueous dispersion medium, the added polar resin can be controlled so that a thin layer is formed on the surface of the toner particles, or that there is an inclination from the toner particle surface toward the center. At this time, by using a polar resin that interacts with the metal phthalocyanines and polymer ligands according to the present invention, while controlling the exposure state of the colorant on the toner particle surface, It is possible to make the presence state of a coloring agent into a desirable form. In particular, it is preferable to use a polar resin having an acid value of 1 to 40 mgKOH / g.

  In the present invention, the addition amount of the polar resin is preferably 1 to 25 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount of the polar resin is less than 1 part by mass, the presence state of the polar resin in the toner particles becomes non-uniform, and conversely if it exceeds 25 parts by mass, the thin layer of the polar resin formed on the toner particle surface becomes thick. In either case, the performance required for the toner cannot be expressed in a well-balanced manner.

  The polar resins as described above are not limited to one type of polymer. For example, two or more types of reactive polyester resins can be used simultaneously, or two or more types of vinyl polymers can be used. Yes, and a completely different kind of polymer, such as non-reactive polyester resin, epoxy resin, polycarbonate resin, polyolefin, polyvinyl acetate, polyvinyl chloride, polyalkyl vinyl ether, polyalkyl vinyl ketone, polystyrene, poly (meth) acrylic Various polymers such as ester, melamine formaldehyde resin, polyethylene terephthalate, nylon and polyurethane can be added to the binder resin as necessary.

  In addition, the toner of the present invention has an average circularity in the circularity frequency distribution of the toner of 0.950 to 0.995, preferably 0.970 to 0.995, so that it has been difficult to control conventionally. The charging characteristics of the toner exhibiting the particle diameter are greatly improved, and good image quality can be maintained even after long-term printing. In particular, when the average circularity is less than 0.950, sufficient transferability cannot be obtained even if the dispersibility of carbon black in the toner is good as in the toner of the present invention. On the other hand, when the average circularity exceeds 0.995, the toner of the present invention tends to cause streaks because the toner is fused to the cleaning blade due to the mutual use of the metal phthalocyanines and the cleaning blade.

  In the present invention, the equivalent circle diameter, circularity, and frequency distribution of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, the flow type particle image measuring device “FPIA” is used. -1000 "(manufactured by Toa Medical Electronics Co., Ltd.) is used for measurement, and is calculated using the following equation.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define.

  The circularity in the present invention is an index indicating the degree of unevenness of the toner, and is 1.000 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where the circularity (center value) at the division point i of the particle size distribution is ci.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) equipped with a 5 mmφ titanium alloy chip as a vibrator is used. To do. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  To measure the shape of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toner particles are obtained. measure. After the measurement, using this data, the equivalent circle diameter of the toner, the circularity frequency distribution, and the like are obtained.

  For the toner of the present invention, known wax components can be used. Specifically, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, and Fischer-Tropsch method. Examples include hydrocarbon waxes and derivatives thereof, polyolefin waxes and derivatives thereof typified by polyethylene, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives include block copolymers with oxides and vinyl monomers. Polymerized products and graft-modified products are also included. Further, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, and animal waxes. These can be used alone or in combination.

  Among these, when polyolefin, Fischer-Tropsch hydrocarbon wax, petroleum wax, higher alcohol, or higher ester is used, the effect of improving developability and transferability is further enhanced. These wax components may be added with an antioxidant within a range that does not affect the chargeability of the toner. Moreover, it is preferable to use 1-30 mass parts of these wax components with respect to 100 mass parts of binder resin.

  The melting point of the wax component used in the present invention is preferably in the range of 30 to 120 ° C., more preferably a wax component having a melting point of 50 to 110 ° C. and a wax component having a melting point of 80 to 140 ° C. are used in combination. Is preferred. At this time, the wax component having a melting point at 50 to 110 ° C. is a polar wax, and the wax component having a melting point at 80 to 140 ° C. is a nonpolar wax, so that the dispersion state of the colorant is not excluded and good fixing is achieved. This is particularly preferred because it can create a state.

  By using the wax component exhibiting the thermal characteristics as described above, not only good fixability of the obtained toner, but also a release effect by the wax component is efficiently expressed, a sufficient fixing area is secured, and conventionally The developability, blocking resistance, and adverse effects on the image forming apparatus due to known wax components can be eliminated. In particular, since the specific surface area of the toner decreases as the toner particle shape becomes spherical, it is very effective to control the thermal characteristics and dispersion state of the wax component.

  The melting point of the wax component used in the present invention means a main endothermic peak temperature in a DSC curve measured according to “ASTM D3418-82”, and is measured by, for example, “DSC-7” (Perkin Elmer). The At this time, the melting point of iridium and zinc is used for the temperature correction of the device detection unit, and the heat of fusion of iridium is used for the correction of the heat quantity. In the measurement, a sample in which the measurement sample was put in an aluminum pan and an aluminum pan only (empty pan) were set for the control, and the measurement range of 20 to 180 ° C. was increased at a heating rate of 10 ° C./min. The melting point is determined from the main endothermic peak temperature of the DSC curve obtained when heated. In the case of measuring only the wax component, the measurement is started after the temperature is raised and lowered under the same conditions as in the measurement to remove the previous history. When measuring the wax component contained in the toner, the measurement is performed as it is without performing the operation of removing the previous history.

  A known charge control agent can be used in combination with the toner of the present invention. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferably used. Further, when the toner particles are directly produced by a polymerization method, a charge control agent having no polymerization inhibitory property and having no solubilized product in an aqueous dispersion medium is preferable. Specific compounds include metal compounds of carboxylic acids such as salicylic acid, naphthoic acid, and dicarboxylic acid as negative charge control agents; polymer compounds having sulfonic acid or carboxylic acid groups in the side chain; boron compounds; urea compounds; Silicon compound; calixarene and the like. Examples of the positive charge control agent include quaternary ammonium salts; polymer type compounds having the quaternary ammonium salt in the side chain; guanidine compounds; imidazole compounds.

  However, in the present invention, it is not essential to add a charge control agent to the toner. When the two-component development method is used, friction charging with the carrier is used. When the non-magnetic one-component blade coating development method is used, friction charging with the blade member or sleeve member is positively performed. Since a sufficient triboelectric charge amount can be obtained by using the toner, it is not always necessary to include other charge control agents in the toner particles.

External addition of the toner inorganic fine powder of the present invention to toner particles is a preferred embodiment for improving the developability, transferability, charging stability, fluidity and durability of the toner. As the inorganic fine powder that can be used in the present invention, publicly known ones can be used, and it is particularly preferred to be selected from silica, alumina, titania, or a double oxide thereof. Further, silica is more preferable. For example, as the silica, both so-called dry silica called fumed silica produced by vapor phase oxidation of silicon halide and alkoxide, and so-called wet silica produced from alkoxide, water glass, etc. can be used. Further, dry silica having less silanol groups on the surface and inside of the silica fine powder and few production residues such as Na ₂ O and SO ₃ ^2- is more preferable. In the dry silica production process, for example, by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds, it is also possible to obtain composite fine powder of silica and other metal oxides, These are also included in the present invention.

Inorganic fine powder used in the present invention has a specific surface area according to the measured nitrogen adsorption by the BET method is 30 m ² / g or more, particularly in the range of 50 to 400 m ² / g give good results. The added amount of the inorganic fine powder is 0.3 to 8 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the toner.

Further, the inorganic fine powder and 170m ² / g inorganic fine powder exhibiting higher specific surface area exhibit a 50 to 150 m ² / g in the range 5: 95-50: By combining with 50 mass ratio of, among the toner particles Since moderate voids and fluidity are imparted to the toner, the charging behavior of the toner is improved, and the effect of controlling the triboelectric charge amount and the charging speed is increased. In addition, it is possible to prevent image defects due to contamination or scraping of the electrostatic latent image carrier or intermediate transfer member due to the colorant. Further, since moderate fluidity is imparted to the toner, the uniform chargeability of the toner is synergistically improved, and the excellent effects as described above are maintained even when a large number of printouts are repeated continuously.

When the specific surface area of the inorganic fine powder is less than 30 m ² / g, it is difficult to impart appropriate fluidity to the toner, and when the specific surface area exceeds 400 m ² / g, Since the inorganic fine powder is embedded in the toner particle surface, the fluidity of the toner may be reduced.

  When the addition amount of the inorganic fine powder is less than 0.3 parts by mass, the effect of addition is not manifested. When the addition amount exceeds 8 parts by mass, not only the charging property and fixing property of the toner are caused, but also the free inorganic Matching with the image forming apparatus is significantly deteriorated by the fine powder.

  In addition, the inorganic fine powder used in the present invention has a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group as necessary for the purpose of hydrophobization and chargeability control. It is possible and preferable to be treated with a treating agent such as a silane coupling agent, an organic silicon compound, or an organic titanium compound, or in combination with various treating agents.

  For the measurement of the specific surface area of the inorganic fine powder, a specific surface area measuring device “Autosorb 1” (manufactured by Yuasa Ionics) is used to adsorb nitrogen gas on the sample surface, and the specific surface area is calculated by the BET multipoint method.

  In order to maintain a high charge amount of the toner and achieve a low consumption and a high transfer rate, the inorganic fine powder is more preferably treated with at least silicone oil.

  In the dry toner of the present invention, other additives such as a lubricant powder such as a polyethylene fluoride powder, a zinc stearate powder, a polyvinylidene fluoride powder; a cerium oxide powder, a silicon carbide, and the like within a range that does not have a substantial adverse effect. Abrasives such as powder and strontium titanate powder; fluidity imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents or electrical conductivity imparting agents such as carbon black powder, zinc oxide powder and tin oxide powder Further, organic fine particles having opposite polarity and inorganic fine particles can be added to the toner particles in small amounts as a developability improver.

  The toner of the present invention can be used not only as a one-component developer without using a carrier but also as a two-component developer by mixing with a carrier.

  When used as a two-component developer, for example, the magnetic carrier to be mixed with the toner is composed of an element selected from iron, copper, zinc, nickel, cobalt, manganese, chromium, etc., alone or in a composite ferrite state. The shape of the magnetic carrier used at this time may be spherical, flat, irregular, or the like, and a magnetic carrier whose surface state fine structure (for example, surface irregularity) is appropriately controlled may be used. it can. A resin-coated carrier whose surface is coated with a resin can also be suitably used. The average particle diameter of the carrier to be used is preferably 10 to 100 μm, more preferably 20 to 50 μm. Further, when the two-component developer is prepared by mixing these carrier and toner, the toner concentration in the developer is preferably 2 to 15% by mass.

  The contents relating to the polymer, carbon black and metal phthalocyanines used in the production of the toner of the present invention are shown in Tables 1 to 3.

<Toner Production Example 1>
As the toner, a polymerization toner was prepared according to the following procedure. 3 parts by weight of tricalcium phosphate is added to 900 g of ion-exchanged water heated to 60 ° C., and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to produce an aqueous medium. did.

Further, the following formulation was put into a TK type homomixer (made by Tokushu Kika Kogyo Co., Ltd.), heated to 60 ° C., then used, stirred at 9,000 rpm, dissolved and dispersed to obtain an aqueous dispersion medium. .
Styrene 80 parts by mass n-butyl acrylate 20 parts by mass Carbon black (1) 7.5 parts by mass Aluminum salicylate compound 0.7 parts by mass (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
Metal phthalocyanines (1) 0.375 parts by mass Polymer R-1-1 0.5 parts by mass Polyester resin 5 parts by mass (Polycondensate of propylene oxide-modified bisphenol A and isophthalic acid, Tg = 65 C, Mw = 10000, Mn = 6000)
-Ester wax (melting point 70 ° C) 5 parts by mass-Fischer-Tropsch wax (melting point 85 ° C) 1 part by mass

  In this, 3 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

  The polymerizable monomer composition was put into the aqueous medium, and granulated by stirring at 8,000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere. Then, the temperature was raised to 70 ° C. over 2 hours while stirring by transferring to a propeller type stirring device, and further 4 hours later, the temperature was raised to 80 ° C. at a rate of temperature rise of 40 ° C./Hr and reacted at 80 ° C. for 5 hours. To produce polymer particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain black toner particles.

  With respect to 100 parts by mass of the black toner particles, 1.5 parts by mass of silica (R972 manufactured by Aerosil Co., Ltd.) was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain the black toner in the present invention. The resulting black toner is referred to as toner (A). Table 4 shows the average circularity of the toner (A) and the value of the frequency of 100 kHz.

<Toner Production Examples 2 to 7>
In Toner Production Example 1, it was produced in the same manner as in Toner Production Example 1 except that the number of added parts of the raw material was not changed and the raw material shown in Table 4 was changed. The average circularity of the toner and the dielectric loss tangent tan δ at a frequency of 100 kHz are also shown.

<Production Examples 1 to 6 for Comparative Toner>
In Toner Production Example 1, it was produced in the same manner as in Toner Production Example 1 except that the number of added parts of the raw material was not changed and the raw material shown in Table 4 was changed. The average circularity of the toner and the dielectric loss tangent tan δ at a frequency of 100 kHz are also shown.

<Production Example 7 for Comparative Toner>
The toner particles obtained in Toner Production Example 1 are spheroidized so that the average circularity of the toner becomes 0.997, and then the same as in Toner Production Example 1 except that silica is mixed. Manufactured. The obtained toner is defined as a toner (g).

<Production Example 8 for Comparative Toner>
Styrene-acrylic copolymer resin (Tg = 60 ° C.) 100 parts by mass Carbon black (1) 7.5 parts by mass Aluminum salicylate compound 0.7 parts by mass (Bontron E-88 manufactured by Orient Chemical Co., Ltd.)
Metal phthalocyanines (1) 0.375 parts by mass Polymer R-1-1 0.5 parts by mass Polyester resin 5 parts by mass (polycondensate of propylene oxide-modified bisphenol A and isophthalic acid, Tg = 65 C, Mw = 10000, Mn = 6000)
-Ester wax (melting point 70 degreeC) 5 mass parts-Fischer-Tropsch wax (melting point 85 degreeC) The mixture which consists of 1 mass part was heat knead | mixed, and after grinding | pulverizing, it classified.

  With respect to 100 parts by mass of the black toner particles, 1.5 parts by mass of silica (R972 manufactured by Aerosil Co., Ltd.) was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain the black toner in the present invention. The obtained black toner is defined as a toner (h). Table 4 shows the average circularity of the toner (h) and the value of the frequency of 100 kHz.

<Example 1>
The full-color image forming apparatus shown in FIG. 1 was used as the image forming apparatus. The developing unit 17 of the process cartridge of the image forming apparatus uses a medium resistance rubber roller made of dimethyl silicone rubber in which carbon black is dispersed and the resistance is adjusted as the toner carrier 15 so as to come into contact with the photosensitive drum 19. The rotational peripheral speed of the developing roller surface is set to 140% in the same direction as the rotational driving of the photosensitive drum at the contact portion with the surface of the photosensitive drum.

  For setting in image formation, first, the image bearing member is uniformly charged by using the charging roller 16 (applying only a direct current component). Subsequent to charging, an image portion is exposed with a laser beam to form an electrostatic latent image, and a visible image is formed with toner, and then the toner image is transferred to a transfer material by a roller to which a voltage of +700 V is applied. The photosensitive member charging potential was set to -580V for the dark portion potential and -150V for the bright portion potential. Further, the applied voltage of the toner carrier 15 at the time of development was only a direct current component (−450 V). The toner amount on the transfer paper was adjusted by changing the voltage applied to the toner carrier 15.

  Further, the fixing device 23 having a heating roller type heating and pressing means shown in FIG. 2, which is not provided with a separation claw or an offset prevention liquid application mechanism, was used.

  For the heating roller 25, after using a cylindrical cored bar made of aluminum as a primer, an elastic layer of dimethyl silicone rubber, and a surface layer made of a PFA tube having a thickness of 50 μm through the primer layer, On the other hand, for the pressure roller 26, a SUS cored bar is primer-treated, and then an elastic layer of dimethyl silicone rubber is provided, and a surface layer is further provided by a PFA tube having a thickness of 50 μm through the primer layer. It was.

  In addition, a halogen heater is provided as a heating element inside the cylindrical core of the heating roller so that the surface temperature of the fixing roller becomes 170 ° C. when the heating and pressing means is operated, and further, the heating roller and the heating roller are heated. A contact pressure of 20 kgf was applied to the pressure roller so that a nip portion having a width of 3 mm was formed.

  The black toner (A) obtained in “Toner Production Example 1” is put into the black toner cartridge of the fourth image forming unit Pd of the above image forming apparatus, and “recycle” is used as a transfer material. Paper EN-100 ”(recycled pulp blending ratio = 100%) was used, and the evaluation of the tinting strength of the toner was evaluated only in the initial stage. For other evaluations, a solid image with an A4 size image ratio of 2% and a toner amount on the transfer paper of 0.3 to 0.35 mg / cm was initially set in the monochrome mode, and then the setting conditions were used. Evaluation was performed after 40,000 sheets were printed out at a printout speed of 32 sheets (A4 size) / min.

  The evaluation contents and evaluation criteria for each evaluation item in printout image evaluation are shown below.

<1> Toner coloring power A solid image is obtained by producing a solid image such that the toner amount on the transfer paper is 0.3 to 0.35 mg / cm ² and the gloss of the image surface after heat and pressure fixing is 20 to 30. The reflection density of the obtained image was measured by “Macbeth reflection densitometer RD918” (manufactured by Macbeth). The obtained measured values were evaluated according to the following evaluation criteria.
A: 1.20 or more B: 1.05 or more and less than 1.20 C: 0.90 or more and less than 1.05 D: Less than 0.90

<2> Image fog When a solid white image is formed, the toner present on the photosensitive drum is taped off with Mylar tape during the transition from the development process to the transfer process, and the reflection density of the image is pasted on paper. Was measured with a “Macbeth reflection densitometer RD918”. Evaluation was performed according to the following evaluation criteria using a numerical value obtained by subtracting the reflection density when the Mylar tape was directly applied to paper from the obtained reflection density. The smaller the numerical value, the more image fog is suppressed.
A: Less than 0.03 B: 0.03 or more and less than 0.07 C: 0.07 or more and less than 1.00 D: 1.00 or more

<3> Image Density A solid solid image having a side of 5 mm was printed on transfer paper (75 g / m ² ), and the reflection density of the printout image was measured by “Macbeth reflection densitometer RD918” (manufactured by Macbeth). The obtained measured values were evaluated according to the following evaluation criteria.
A: 1.40 or more B: 1.35 or more and less than 1.40 C: 1.00 or more and less than 1.35 D: less than 1.00

<4> Transferability The residual toner on the photosensitive member at the time of solid image formation is taped and peeled off with Mylar tape, and the reflection density of the toner stuck on paper is measured with a “Mugbes reflection densitometer RD918”. The obtained reflection density was evaluated using a value obtained by subtracting the reflection density when the Mylar tape was stuck on paper as it was. The smaller the value, the better the transferability.
A: Less than 0.03 B: 0.03 or more, less than 0.07 C: 0.07 or more, less than 0.10 D: 0.10 or more

<5> Image streaks due to poor cleaning A halftone image was printed out, and the number of occurrences of vertical stripe-like image density unevenness generated on the image was measured and evaluated according to the following evaluation criteria.
A: Not generated B: One minor vertical line is generated C: 2 to 4 D: 5 or more

  When the printout image obtained according to the above was evaluated, generally good results were obtained for each evaluation item. These evaluation results are shown in Table 5.

<Example 2>
In Example 1, evaluation was performed in the same manner as in Example 1 except that evaluation was performed using toner (B). As a result, good results were obtained for each evaluation item. These results are shown in Table 5.

<Example 3>
In Example 1, evaluation was performed in the same manner as in Example 1 except that evaluation was performed using toner (C). As a result, the transferability was deteriorated. This is considered to be because carbon black having a small DBP oil absorption was used. These results are shown in Table 5.

<Example 4>
In Example 1, evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using toner (D). As a result, although transferability was deteriorated, it was a level with no problem. This is considered to be because carbon black having a large DBP oil absorption was used. These results are shown in Table 5.

<Example 5>
In Example 1, evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using toner (E). As a result, although the image density was deteriorated, it was a problem-free level. This is probably because carbon black having a low pH was used. These results are shown in Table 5.

<Example 6>
In Example 1, evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using toner (F). As a result, although the image density was deteriorated, it was a problem-free level. This is probably because carbon black having a high pH was used. These results are shown in Table 5.

<Example 7>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using toner (G). As a result, although fog, image density, and transferability were inferior, there was no problem. This is considered to be because the chargeability of the toner was inferior because metal phthalocyanine having low styrene solubility was used. These results are shown in Table 5.

<Comparative Example 1>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (a). As a result, toner coloring power and transferability were significantly deteriorated. This is probably because a polymer having a low BMAM content was used. These results are shown in Table 5.

<Comparative example 2>
In Example 1, evaluation was performed in the same manner as in Example 1 except that evaluation was performed using toner (b). As a result, the transferability was remarkably deteriorated. This is presumably because a polymer having a high BMAM content was used. These results are shown in Table 5.

<Comparative Example 3>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (c). As a result, toner coloring power, fog, image density and transferability were remarkably deteriorated. This is considered to be because carbon black with a large amount of toluene extraction was used. These results are shown in Table 5.

<Comparative example 4>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (d). As a result, toner coloring power, fog, image density and transferability were remarkably deteriorated. This is considered to be due to the use of metal phthalocyanine that does not dissolve in styrene. These results are shown in Table 5.

<Comparative Example 5>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (e). As a result, toner coloring power, fog, image density and transferability were remarkably deteriorated. This is considered to be because a polymer is not added. These results are shown in Table 5.

<Comparative Example 6>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (f). As a result, toner coloring power, fog, image density and transferability were remarkably deteriorated. This is considered to be because a polymer is not added. These results are shown in Table 5.

<Comparative Example 7>
In Example 1, the evaluation was performed in the same manner as in Example 1 except that the evaluation was performed using the toner (g). As a result, the level of image streaks due to poor cleaning deteriorated significantly. This is considered to be because the toner having a large average circularity was used. These results are shown in Table 5.

<Comparative Example 8>
In Example 1, evaluation was performed in the same manner as in Example 1 except that evaluation was performed using toner (h). As a result, transferability was remarkably deteriorated. This is considered to be because a toner having a small average circularity was used. These results are shown in Table 5.

FIG. 2 is a schematic explanatory diagram illustrating an example of a configuration of a full-color image forming apparatus that can suitably use the toner of the present invention. It is a schematic explanatory drawing of an example of the heating-pressurizing means of a heat roller system preferably used in the present invention.

Explanation of symbols

Pa, Pb, Pc, Pd Image forming unit 15 Developer carrier (developing roller)
Reference Signs List 16 charging roller 17 developing device 19 photoconductor 20 transfer belt 23 fixing device S transfer material

Claims (8)

At least in a toner having a binder resin, carbon black, wax component, metal phthalocyanine and / or metal phthalocyanine derivative,
A polymer containing 0.5 to 20% by mass of a polymerizable monomer represented by the following structural formula (1) and / or (2) as a constituent unit, or a polymerizability represented by the following structural formula (3) Containing a polymer containing 0.5 to 20% by mass of a monomer and a carboxyl group-containing vinyl monomer each as a constituent unit;
The toluene extraction amount of the carbon black is 0.2% by mass or less,
The solubility in styrene at 25 ° C. of the metal phthalocyanine and / or metal phthalocyanine derivative is 3% by mass or more,
A toner having an average circularity of 0.950 to 0.995 and a dielectric loss tangent tan δ measured at a frequency of 100 kHz of 0.002 to 0.015.

(In the structural formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ and R ₃ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. X ₁ represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium salt, and n represents an integer of 1 to 10.)

(In the structural formula (2), R ₄ represents a hydrogen atom or a methyl group, and R _{5 to} R ₈ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, an alkoxy group, respectively. Or an aromatic group, at least one of which represents an unsubstituted or substituted aromatic group, X ₂ represents a hydrogen atom, an alkali metal, an alkaline earth metal, or a quaternary ammonium salt; Represents an integer of -10.)

(In the structural formula (3), R ₉ represents a hydrogen atom or a methyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, a C ₁ -C ₂₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. R ₁₀ and R ₁₁ may be chemically bonded to form a non-aromatic organic group that forms a C _{4 to} C ₂₀ cyclic structure having a hetero atom other than a carbon atom.   The toner according to claim 1, wherein a dielectric loss tangent tan δ measured at a frequency of 100 kHz is 0.002 to 0.008.   The toner according to claim 1, wherein the toner has an average circularity of 0.970 to 0.995.   The toner according to claim 1, wherein the metal phthalocyanine and / or the metal phthalocyanine derivative has a solubility in styrene at 25 ° C. of 5% by mass or more.   The toner according to claim 1, wherein the metal phthalocyanine and / or metal phthalocyanine derivative is a metal compound selected from Cr, Fe, Co, Ni, Zn, Mn, Mg, and Al.   The toner according to claim 1, wherein the metal phthalocyanine and / or the metal phthalocyanine derivative is a Zn compound.   The toner according to claim 1, wherein the carbon black has a pH of 5.5 to 10.5.   The toner according to claim 1, wherein the carbon black has a DBP oil absorption of 20 to 150 ml / 100 g.

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