JP2015075601A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which shows excellent fixability even in high-speed printing, which is free of thinning in an initial state as well as after long-term use, and which has excellent printing durability and thin line reproducibility and good storage property.SOLUTION: The toner for electrostatic charge image development comprises colored resin particles comprising a binder resin and a colorant, and an external additive. The external additive comprises, with respect to 100 parts by mass of the colored resin particles: 0.05 to 1.5 parts by mass of nitrogen-containing resin particles having a number average primary particle diameter of 10 to 150 nm; 0.2 to 3.0 parts by mass of inorganic fine particles (A) having a number average primary particle diameter of 31 to 300 nm; 0.1 to 2.0 parts by mass of inorganic fine particles (B) having a number average primary particle diameter of 11 to 30 nm; and 0.1 to 1.0 part by mass of inorganic fine particles (C) having a number average primary particle diameter of 5 to 10 nm.

Description

  The present invention relates to a toner that can be used for development of an image forming apparatus using electrophotography such as a copying machine, a facsimile machine, and a printer.

  Conventionally, in a developer used for general electrophotography, desired fluidity and charging characteristics can be obtained by attaching an external additive to the surface of the colored resin particles. As the external additive, fine particles made of inorganic or organic substances are widely used. As such an external additive, metal oxide particles and resin particles, and those obtained by surface treatment of these have been widely used. In general, metal oxide particles such as silica, titania and alumina are often used, but organic fine particles composed of methyl methacrylate polymer, polystyrene, polyester resin, silicone resin, etc. are also used. .

  In addition to the organic fine particles described above, Patent Document 1 includes a colored fine particle having a sphericity of 0.8 or more and a primary average particle size of 30 to 30 containing a binder resin made of a styrene resin and a colorant. A non-magnetic one-component developer obtained by mixing silica fine particles of 100 nm and triazine resin fine particles made of a condensation polymer is disclosed. Patent Document 2 discloses that at least colored particles composed of a resin and a colorant, resin fine particles composed of a melamine / formaldehyde condensation polymer having a volume average particle diameter of 0.01 to 1.0 μm, and a volume average particle diameter of 0.01. An electrophotographic image forming toner to which inorganic fine particles of .about.0.2 .mu.m are added is disclosed.

JP-A-7-114214 JP-A-8-314182

  However, with the toner of the above-mentioned patent document, the storage temperature cannot be ensured while keeping the fixing temperature low in recent high-speed printing, and the printing durability and anti-scratch prevention may not be sufficient.

  The object of the present invention is to solve the above-mentioned problems, excellent in fixing property even in high-speed printing, no generation of blurring after the initial and durability, excellent in printing durability and fine line reproducibility, and excellent in storage stability. Is to provide.

  As a result of intensive studies to solve the above problems, the inventor of the present invention uses an external additive that combines nitrogen-containing resin particles having a specific particle diameter and three kinds of inorganic fine particles having different particle diameters. It was found that the above problem can be solved.

  That is, according to the present invention, in the toner for electrostatic charge development containing a colored resin particle containing a binder resin and a colorant, and an external additive, the external additive is based on 100 parts by mass of the colored resin particles. 0.05 to 1.5 parts by mass of nitrogen-containing resin particles having a number average primary particle size of 10 to 150 nm, 0.2 to 3.0 parts by mass of inorganic fine particles A having a number average primary particle size of 31 to 300 nm, 0.1 to 2.0 parts by mass of inorganic fine particles B having a number average primary particle size of 11 to 30 nm and 0.1 to 1.0 parts by mass of inorganic fine particles C having a number average primary particle size of 5 to 10 nm An electrostatic charge image developing toner is provided.

  In the external additive of the present invention, the adsorbed water amounts of the inorganic fine particles A, the inorganic fine particles B, and the inorganic fine particles C are 0.1 to 0.4% by mass, 0.1 to 0.6% by mass, and 0.0. It is preferable that it is 1-1.0 mass%.

  In the external additive of the present invention, the total content of the inorganic fine particles A, the inorganic fine particles B, and the inorganic fine particles C is preferably 1.2 to 4.0 parts by mass with respect to 100 parts by mass of the colored resin particles. .

  The external additive in the present invention preferably further contains fatty acid metal salt particles having a number average primary particle size of 100 to 2,000 nm.

  In the external additive of the present invention, the surface of each of the inorganic particle microparticles A, inorganic particle microparticles B, and inorganic particle microparticles C is preferably treated with a hydrophobizing agent containing an amino group. .

  According to the toner of the present invention as described above, in addition to nitrogen-containing resin particles having a specific particle size, inorganic fine particles A, inorganic fine particles B and inorganic fine particles C having different number average primary particle sizes are used in combination as an external additive. As a result, the toner can be improved in fixability, storage stability, printing durability, and fine line reproducibility, and at the same time, it is possible to provide a toner that does not easily cause blurring or fogging.

  The toner for developing an electrostatic charge image of the present invention is a toner for developing an electrostatic charge containing a colored resin particle containing a binder resin and a colorant, and an external additive. The external additive is 100 masses of the colored resin particles. Parts by weight of the nitrogen-containing resin particles having a number average primary particle size of 10 to 150 nm and 0.05 to 1.5 parts by mass of inorganic fine particles A having a number average primary particle size of 31 to 300 nm. 0.1 to 2.0 parts by mass of inorganic fine particles B having a mass average number average primary particle size of 11 to 30 nm and 0.1 to 1.0 mass of inorganic fine particles C having a number average primary particle size of 5 to 10 nm Part, containing.

Hereinafter, the toner for developing an electrostatic charge image of the present invention (hereinafter sometimes simply referred to as “toner”) will be described.
The toner of the present invention contains colored resin particles containing a binder resin and a colorant, and an external additive.
Hereinafter, the manufacturing method of the colored resin particles used in the present invention, the colored resin particles obtained by the manufacturing method, the manufacturing method of the toner of the present invention using the colored resin particles, and the toner of the present invention will be described in order.

1. Production method of colored resin particles Generally, the production method of colored resin particles is roughly classified into dry methods such as a pulverization method, and wet methods such as an emulsion polymerization aggregation method, a suspension polymerization method, and a dissolution suspension method. The wet method is preferable because it is easy to obtain a toner excellent in printing characteristics such as the property. Among wet methods, a polymerization method such as an emulsion polymerization aggregation method and a suspension polymerization method is preferable because a toner having a relatively small particle size distribution on the order of microns is preferable. A suspension polymerization method is more preferable among polymerization methods. preferable.

  In the emulsion polymerization aggregation method, an emulsified polymerizable monomer is polymerized to obtain a resin fine particle emulsion, which is aggregated with a colorant dispersion or the like to produce colored resin particles. The dissolution suspension method produces droplets of a solution in which toner components such as a binder resin and a colorant are dissolved or dispersed in an organic solvent in an aqueous medium, and the organic solvent is removed to produce colored resin particles. Each of which is a known method.

  The colored resin particles of the present invention can be produced by employing a wet method or a dry method. Among the wet methods, a preferred suspension polymerization method is adopted, and the following process is performed.

(A) Suspension polymerization method (A-1) Preparation step of polymerizable monomer composition First, other additions such as a polymerizable monomer, a colorant, and a release agent added as necessary The product is mixed to prepare a polymerizable monomer composition. The mixing at the time of preparing the polymerizable monomer composition is performed using, for example, a media type dispersing machine.

  In the present invention, the polymerizable monomer means a monomer having a polymerizable functional group, and the polymerizable monomer is polymerized to become a binder resin. It is preferable to use a monovinyl monomer as the main component of the polymerizable monomer. Examples of the monovinyl monomer include styrene; styrene derivatives such as vinyl toluene and α-methylstyrene; acrylic acid and methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic acid 2 Acrylic esters such as ethylhexyl and dimethylaminoethyl acrylate; methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and dimethylaminoethyl methacrylate; acrylonitrile And nitrile compounds such as methacrylonitrile; amide compounds such as acrylamide and methacrylamide; and olefins such as ethylene, propylene, and butylene. These monovinyl monomers can be used alone or in combination of two or more. Of these, styrene, styrene derivatives, and acrylic esters or methacrylic esters are preferably used as monovinyl monomers.

In order to improve hot offset and storage stability, it is preferable to use any crosslinkable polymerizable monomer together with the monovinyl monomer. A crosslinkable polymerizable monomer means a monomer having two or more polymerizable functional groups. Examples of the crosslinkable polymerizable monomer include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; alcohols having two or more hydroxyl groups such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate; Ester compounds in which two or more carboxylic acids having a carbon-carbon double bond are ester-bonded; other divinyl compounds such as N, N-divinylaniline and divinyl ether; compounds having three or more vinyl groups; Can be mentioned. These crosslinkable polymerizable monomers can be used alone or in combination of two or more.
In the present invention, the crosslinkable polymerizable monomer is usually used at a ratio of 0.1 to 5 parts by mass, preferably 0.3 to 2 parts by mass with respect to 100 parts by mass of the monovinyl monomer. desirable.

  Furthermore, it is preferable to use a macromonomer as a part of the polymerizable monomer because the balance between the storage stability of the obtained toner and the fixing property at low temperature is improved. The macromonomer has a polymerizable carbon-carbon unsaturated double bond at the end of the molecular chain, and is a reactive oligomer or polymer having a number average molecular weight of usually 1,000 to 30,000. The macromonomer is preferably one that gives a polymer having a higher Tg than the glass transition temperature of the polymer obtained by polymerizing the monovinyl monomer (hereinafter sometimes referred to as “Tg”). The macromonomer is preferably used in an amount of 0.03 to 5 parts by mass, more preferably 0.05 to 1 part by mass, with respect to 100 parts by mass of the monovinyl monomer.

In the present invention, a colorant is used. However, when producing a color toner, black, cyan, yellow, and magenta colorants can be used.
As the black colorant, for example, carbon black, titanium black, magnetic powder such as zinc zinc oxide and nickel iron oxide can be used.

  As the cyan colorant, for example, a copper phthalocyanine compound, a derivative thereof, and an anthraquinone compound can be used. Specifically, C.I. I. Pigment blue 2, 3, 6, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17: 1, 60, and the like.

  Examples of the yellow colorant include monoazo pigments, azo pigments such as disazo pigments, and compounds such as condensed polycyclic pigments. I. Pigment yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, and 213.

  Examples of the magenta colorant include compounds such as monoazo pigments, azo pigments such as disazo pigments, and condensed polycyclic pigments. I. Pigment Red 31, 48, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 184, 185, 187, 202, 206, 207, 209, 237, 238, 251, 254, 255, 269 and C.I. I. Pigment violet 19 and the like.

  In the present invention, each colorant can be used alone or in combination of two or more. The amount of the colorant is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the monovinyl monomer.

  As other additives, a release agent can be added to the polymerizable monomer composition from the viewpoint of improving the releasability of the toner from the fixing roll during fixing. Any releasing agent can be used without particular limitation as long as it is generally used as a releasing agent for toner.

  The release agent preferably contains an ester wax and / or a hydrocarbon wax. By using these waxes as a release agent, the balance between low-temperature fixability and heat-resistant storage stability can be made suitable.

The ester wax suitably used as a release agent in the present invention is more preferably a polyfunctional ester wax, for example, a pentaerythritol ester such as pentaerythritol tetrapalmitate, pentaerythritol tetrabehenate, pentaerythritol tetrastearate, etc. Compound: hexaglycerin tetrabehenate tetrapalmitate, hexaglycerin octabehenate, pentaglycerin heptabehenate, tetraglycerin hexabehenate, triglycerin pentabehenate, diglycerin tetrabehenate, glycerin tribe Glycerin ester compounds such as henate; Dipentaerythritol ester compounds such as dipentaerythritol hexamyristate and dipentaerythritol hexapalmitate; It is.
The ester wax is preferably used in an amount of 2 to 10 parts by weight, more preferably 3 to 7 parts by weight, based on 100 parts by weight of the monovinyl monomer.
The melting point of the ester wax is usually 50 to 90 ° C, preferably 60 to 85 ° C, more preferably 65 to 75 ° C.

Examples of the hydrocarbon wax suitably used as a release agent in the present invention include polyethylene wax and polyolefin wax such as polypropylene wax; Fischer-Tropsch wax; petroleum wax such as paraffin wax and microstalline wax. Fischer-Tropsch wax and petroleum wax are preferable, petroleum wax is more preferable, and paraffin wax is particularly preferable.
The number average molecular weight of the hydrocarbon wax is preferably 300 to 800, more preferably 400 to 600. Moreover, the penetration of the hydrocarbon wax measured by JIS K2235 5.4 is preferably 1 to 10, and more preferably 2 to 7.
The hydrocarbon wax is preferably used in an amount of 0.5 to 8 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the monovinyl monomer.
The melting point of the hydrocarbon wax is usually 40 to 100 ° C, preferably 50 to 80 ° C, more preferably 60 to 75 ° C.

In addition to the mold release agent, for example, natural wax such as jojoba; mineral wax such as ozokerite;
The release agent is preferably used in combination of one or more waxes as described above.
The total content of the release agent is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the monovinyl monomer.

As other additives, a positively or negatively chargeable charge control agent can be used to improve the chargeability of the toner.
The charge control agent is not particularly limited as long as it is generally used as a charge control agent for toner, but among charge control agents, the compatibility with the polymerizable monomer is high, and stable chargeability. (Charge stability) can be imparted to the toner particles, and therefore a positively or negatively chargeable charge control resin is preferred. Further, from the viewpoint of obtaining a positively chargeable toner, a positively chargeable charge control resin More preferably used. The toner of the present invention is preferably a positively chargeable toner.
Examples of positively chargeable charge control agents include nigrosine dyes, quaternary ammonium salts, triaminotriphenylmethane compounds and imidazole compounds, polyamine resins as charge control resins that are preferably used, and quaternary ammonium group-containing copolymers. , And quaternary ammonium base-containing copolymers.
Negatively chargeable charge control agents include azo dyes containing metals such as Cr, Co, Al, and Fe, salicylic acid metal compounds and alkylsalicylic acid metal compounds, and sulfonic acid group containing charge control resins that are preferably used Examples thereof include a copolymer, a sulfonate group-containing copolymer, a carboxylic acid group-containing copolymer, and a carboxylic acid group-containing copolymer.
In the present invention, the charge control agent is usually used in a proportion of 0.01 to 10 parts by mass, preferably 0.03 to 8 parts by mass, with respect to 100 parts by mass of the monovinyl monomer. If the addition amount of the charge control agent is less than 0.01 parts by mass, fog may occur. On the other hand, when the addition amount of the charge control agent exceeds 10 parts by mass, printing stains may occur.

As other additives, it is preferable to use a molecular weight modifier when polymerizing a polymerizable monomer that is polymerized to become a binder resin.
The molecular weight modifier is not particularly limited as long as it is generally used as a molecular weight modifier for toner. For example, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2,2, Mercaptans such as 4,6,6-pentamethylheptane-4-thiol; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, N, N′-dimethyl-N, N′-diphenylthiuram disulfide, N, And thiuram disulfides such as N′-dioctadecyl-N, N′-diisopropylthiuram disulfide; These molecular weight modifiers may be used alone or in combination of two or more.
In this invention, it is desirable to use a molecular weight modifier in the ratio of 0.01-10 mass parts normally with respect to 100 mass parts of monovinyl monomers, Preferably it is 0.1-5 mass parts.

(A-2) Suspension step for obtaining a suspension (droplet formation step)
In the present invention, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is dispersed in an aqueous medium containing a dispersion stabilizer, a polymerization initiator is added, and then the polymerizable monomer is added. A droplet of the composition is formed. The method for forming droplets is not particularly limited. For example, (in-line type) emulsifying disperser (trade name: Milder, manufactured by Taiheiyo Kiko Co., Ltd.), high-speed emulsifying disperser (manufactured by PRIMIX, trade name: TK Homomixer MARK Using a device capable of strong stirring, such as type II).

  As a polymerization initiator, persulfates such as potassium persulfate and ammonium persulfate: 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-methyl-N- (2- Hydroxyethyl) propionamide), 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobisisobutyronitrile Azo compounds such as: di-t-butyl peroxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxydiethyl acetate, t-hexylperoxy-2-ethylbutanoate Diisopropyl peroxydicarbonate, di-t-butylperoxyisophthalate, and t-butylperoxyiso Organic peroxides such as Chireto like. These can be used alone or in combination of two or more. Among these, it is preferable to use an organic peroxide because residual polymerizable monomers can be reduced and printing durability is excellent.

  Among organic peroxides, peroxyesters are preferable because non-aromatic peroxyesters, that is, peroxyesters having no aromatic ring, are preferable because initiator efficiency is good and the amount of remaining polymerizable monomers can be reduced. More preferred.

  As described above, the polymerization initiator may be added before the droplet formation after the polymerizable monomer composition is dispersed in the aqueous medium. However, the polymerization initiator is not dispersed in the aqueous medium. It may be added to the monomer composition.

  The addition amount of the polymerization initiator used for the polymerization of the polymerizable monomer composition is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 100 parts by mass of the monovinyl monomer. It is -15 mass parts, Most preferably, it is 1-10 mass parts.

  In the present invention, the aqueous medium refers to a medium containing water as a main component.

  In the present invention, the aqueous medium preferably contains a dispersion stabilizer. Examples of the dispersion stabilizer include sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; metals such as aluminum oxide and titanium oxide. Oxides; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; inorganic compounds such as; water-soluble polymers such as polyvinyl alcohol, methylcellulose, and gelatin; anionic surfactants; Organic compounds such as nonionic surfactants; amphoteric surfactants; The said dispersion stabilizer can be used 1 type or in combination of 2 or more types.

  Among the above dispersion stabilizers, inorganic compounds, particularly colloids of poorly water-soluble metal hydroxides are preferred. By using a colloid of an inorganic compound, particularly a poorly water-soluble metal hydroxide, the particle size distribution of the colored resin particles can be narrowed, and the residual amount of the dispersion stabilizer after washing can be reduced. The toner thus produced can reproduce the image clearly and has excellent environmental stability.

(A-3) Polymerization step As in (A-2) above, droplet formation is performed, the resulting aqueous dispersion medium is heated to initiate polymerization, and an aqueous dispersion of colored resin particles is formed.
The polymerization temperature of the polymerizable monomer composition is preferably 50 ° C. or higher, more preferably 60 to 95 ° C. The polymerization reaction time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

  The colored resin particles may be used as a polymerized toner by adding an external additive as it is, but the so-called core-shell type obtained by using the colored resin particles as a core layer and forming a shell layer different from the core layer on the outside thereof. It is preferable to use colored resin particles (also referred to as “capsule type”). The core-shell type colored resin particles balance the reduction of the fixing temperature and the prevention of aggregation during storage by coating the core layer made of a material having a low softening point with a material having a higher softening point. be able to.

  There is no restriction | limiting in particular as a method of manufacturing a core shell type colored resin particle using the said colored resin particle mentioned above, It can manufacture by a conventionally well-known method. An in situ polymerization method and a phase separation method are preferable from the viewpoint of production efficiency.

A method for producing core-shell type colored resin particles by in situ polymerization will be described below.
Addition of a polymerizable monomer (polymerizable monomer for shell) and a polymerization initiator to form a shell layer into an aqueous medium in which colored resin particles are dispersed, and then polymerize to form a core-shell type color. Resin particles can be obtained.

  As the polymerizable monomer for the shell, the same monomers as the aforementioned polymerizable monomers can be used. Among them, it is preferable to use monomers such as styrene, acrylonitrile, and methyl methacrylate, which can obtain a polymer having a Tg exceeding 80 ° C., alone or in combination of two or more.

  As a polymerization initiator used for polymerization of the polymerizable monomer for shell, persulfate metal salts such as potassium persulfate and ammonium persulfate; 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) Water-soluble such as azo initiators such as) propionamide) and 2,2′-azobis- (2-methyl-N- (1,1-bis (hydroxymethyl) 2-hydroxyethyl) propionamide); A polymerization initiator can be mentioned. These can be used alone or in combination of two or more. The amount of the polymerization initiator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer for shell.

  The polymerization temperature of the shell layer is preferably 50 ° C. or higher, more preferably 60 to 95 ° C. The polymerization reaction time is preferably 1 to 20 hours, more preferably 2 to 15 hours.

(A-4) Washing, filtration, dehydration, and drying steps The aqueous dispersion of colored resin particles obtained by polymerization is washed, dehydrated, and filtered to remove the dispersion stabilizer according to a conventional method after completion of the polymerization. The drying operation is preferably repeated several times as necessary.

  As the above washing method, when an inorganic compound is used as the dispersion stabilizer, the dispersion stabilizer can be dissolved in water and removed by adding an acid or alkali to the aqueous dispersion of colored resin particles. preferable. When a colloid of a poorly water-soluble inorganic hydroxide is used as the dispersion stabilizer, it is preferable to adjust the pH of the colored resin particle aqueous dispersion to 6.5 or less by adding an acid. As the acid to be added, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as formic acid and acetic acid can be used. Particularly, since the removal efficiency is large and the burden on the manufacturing equipment is small, Sulfuric acid is preferred.

  Various known methods and the like can be used as the method of dehydration and filtration, and there is no particular limitation. Examples thereof include a centrifugal filtration method, a vacuum filtration method, and a pressure filtration method. Also, the drying method is not particularly limited, and various methods can be used.

(B) Pulverization method When the pulverization method is used to produce colored resin particles, the following process is performed.
First, a binder resin, a colorant, and other additives such as a release agent added as needed are mixed in a mixer such as a ball mill, a V-type mixer, an FM mixer (trade name, Nippon Coke Industries, Ltd.). ), High-speed dissolver, internal mixer, Fallberg, etc. Next, the mixture obtained as described above is kneaded while being heated using a pressure kneader, a twin-screw extrusion kneader, a roller or the like. The obtained kneaded material is coarsely pulverized using a pulverizer such as a hammer mill, a cutter mill, or a roller mill. Furthermore, after finely pulverizing using a pulverizer such as a jet mill or a high-speed rotary pulverizer, it is classified into a desired particle size by a classifier such as an air classifier or an airflow classifier, and colored resin particles obtained by a pulverization method. Get.

  In addition, as the binder resin used in the pulverization method, the colorant, and other additives such as a release agent added if necessary, those mentioned in the above (A) suspension polymerization method may be used. it can. Further, the colored resin particles obtained by the pulverization method can be made into core-shell type colored resin particles by a method such as an in situ polymerization method in the same manner as the colored resin particles obtained by the suspension polymerization method (A) described above.

  As the binder resin, other resins that have been widely used for toners can be used. Specific examples of the binder resin used in the pulverization method include polystyrene, styrene-butyl acrylate copolymer, polyester resin, and epoxy resin.

2. Colored resin particles Colored resin particles are obtained by a production method such as the above-described (A) suspension polymerization method or (B) pulverization method.
Hereinafter, the colored resin particles constituting the toner will be described. The colored resin particles described below include both core-shell type and non-core type.

  The volume average particle diameter (Dv) of the colored resin particles is preferably 4 to 12 μm, more preferably 5 to 10 μm, still more preferably 7.8 to 8.8 μm, and particularly preferably 7.9 to It is 8.7 μm, and most preferably 8.0 to 8.6 μm. When Dv is less than 4 μm, the fluidity of the toner is lowered, the transferability may be deteriorated, and the image density may be lowered. When Dv exceeds 12 μm, the resolution of the image may decrease.

  The colored resin particles have a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of preferably 1.0 to 1.3, more preferably 1. 0-1.2. If Dv / Dn exceeds 1.3, transferability, image density, and resolution may decrease. The volume average particle diameter and the number average particle diameter of the colored resin particles can be measured using, for example, a particle size analyzer (trade name: Multisizer, manufactured by Beckman Coulter).

From the viewpoint of image reproducibility, the average circularity of the colored resin particles of the present invention is preferably 0.96 to 1.00, more preferably 0.97 to 1.00, and 0.98 to More preferably, it is 1.00.
When the average circularity of the colored resin particles is less than 0.96, the fine line reproducibility of printing may be deteriorated.

  In the present invention, the circularity is defined as a value obtained by dividing the circumference of a circle having the same projected area as the particle image by the circumference of the projected image of the particle. The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles, and is an index indicating the degree of unevenness of the colored resin particles. The average circularity is determined by the colored resin particles. 1 is shown in the case of a perfect sphere, and the value becomes smaller as the surface shape of the colored resin particles becomes more complicated.

3. Toner Production Method In the present invention, the colored resin particles are mixed and stirred together with an external additive and subjected to an external addition treatment, whereby the external additive is adhered to the surface of the colored resin particles to develop a one-component toner (development). Agent). The one-component toner may be further mixed and stirred together with carrier particles to form a two-component developer.

  The stirrer that performs the external addition treatment is not particularly limited as long as the stirrer can attach the external additive to the surface of the colored resin particles. For example, an FM mixer (trade name, manufactured by Nippon Coke Kogyo Co., Ltd.), Super Mixer (: trade name, manufactured by Kawada Seisakusho Co., Ltd.), Q mixer (: trade name, manufactured by Nihon Coke Kogyo Co., Ltd.), mechano-fusion system (: trade name, manufactured by Hosokawa Micron), and mechano mill (: trade name, manufactured by Okada Seiko Co., Ltd.) The external addition treatment can be performed using a stirrer capable of mixing and stirring.

  The toner of the present invention contains at least nitrogen-containing resin particles, inorganic fine particles A, inorganic fine particles B, and inorganic fine particles C as external additives. Hereinafter, these external additives will be described in order.

The nitrogen-containing resin particles used as an external additive in the present invention are particles having a number average primary particle size of 10 to 150 nm made of a resin containing a nitrogen element.
The nitrogen-containing resin particles in the present invention are specifically selected from the group consisting of benzoguanamine, cyclohexanecarboguanamine, cyclohexenecarboguanamine, melamine, acetoguanamine, norbornenecarboguanamine, paratoluenesulfonamide and urea. Particles obtained by reacting at least one nitrogen-containing compound with formaldehyde are preferable.

  As the nitrogen-containing resin particles, commercially available ones can be used, but they can be produced by a known method. For example, the nitrogen-containing compound and formaldehyde are reacted (addition condensation reaction) to obtain an amino resin precursor that is an initial condensate, and the obtained precursor is added to an aqueous solution in which a surfactant is dissolved. Obtain an emulsion. Next, an acidic catalyst is added to the emulsion to condense and cure the precursor, and then the cured resin is separated from the emulsion after the reaction, washed with water, and then at a high temperature of 100 to 200 ° C. The particles made of a nitrogen-containing resin are formed by drying. Usually, this reaction is carried out under heating (50 to 100 ° C.), and in order to increase the degree of crosslinking, the separated cured resin is dispersed again in an aqueous solution in which the surfactant is dissolved as necessary, and the acidic catalyst is further added. It can also be added and repeated condensation and curing. The particle size of the nitrogen-containing resin particles obtained by the above method can be controlled by the amount of the surfactant used.

The number average primary particle size of the nitrogen-containing resin particles is 10 to 150 nm. When the number average primary particle size is less than 10 nm, precise control of the particle size may be difficult. On the other hand, when the number average primary particle size exceeds 150 nm, the fluidity is remarkably lowered and the scum is greatly deteriorated compared to the case where the number average primary particle size is 150 nm or less. In this case, the effect of improving the charge amount is reduced, and there are cases where the printing durability and the effect of improving fog in a high temperature and high humidity environment are not observed.
The number average primary particle size of the nitrogen-containing resin particles is more preferably 30 to 130 nm, and further preferably 50 to 100 nm.

The number-average primary particle size of the nitrogen-containing resin particles, inorganic fine particles A, inorganic fine particles B, and inorganic fine particles C used in the present invention and the fatty acid metal salt particles suitably used in the present invention is, for example, as follows: Can be measured. First, the particle size of each particle of these external additives is measured with a transmission electron microscope (TEM), a scanning electron microscope (SEM), or the like. Thus, the particle diameter of 30 or more external additive particles is measured, and the average value is defined as the number average primary particle diameter of the particles.
As another method for measuring the number average primary particle size of these external additives used in the present invention, the external additive particles are dispersed in a dispersion medium such as water, and the dispersion is measured with a particle size distribution measuring device ( Examples include a method of measuring the number average primary particle diameter by a method of measuring by Nikkiso, trade name: Microtrac 3300EXII) and the like.

The content of the nitrogen-containing resin particles is usually 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the colored resin particles, and preferably 0.2 to 1.0 parts by mass, More preferably, it is -0.7 mass part.
When the content of the nitrogen-containing resin particles is less than 0.05 parts by mass, the charge amount of the toner using the nitrogen-containing resin particles may decrease, resulting in a decrease in toner printing durability and fine line reproducibility. . On the other hand, when the content of the nitrogen-containing resin particles exceeds 1.5 parts by mass, the toner using the nitrogen-containing resin particles may be likely to be blurred or fogged.

By using the nitrogen-containing resin particles as an external additive, the chargeability of the toner can be raised, printing durability, and fogging in a high temperature and high humidity environment can be improved. In addition, the effect on fine line reproducibility in low-temperature and low-humidity environments is small compared to the case where the charge amount is controlled by a so-called internal additive such as a charge control resin, and as a result, the environmental stability of the toner can be greatly enhanced. .
However, when only nitrogen-containing resin particles are used as an external additive, the fluidity may be deteriorated. Therefore, the combined use with inorganic fine particles A, inorganic fine particles B, and inorganic fine particles C described later is indispensable.

In the present invention, inorganic fine particles A having a number average primary particle size of 31 to 300 nm are contained as external additives. When the number average primary particle size of the inorganic fine particles A is less than 31 nm, the spacer effect is lowered, and the inorganic fine particles B and C, which will be described later, are easily embedded from the surface of the colored resin particles, and printing such as generation of fog Adversely affects performance. On the other hand, when the number average primary particle size of the inorganic fine particles A exceeds 300 nm, the inorganic fine particles A are easily released from the surface of the toner particles, the function as an external additive is lowered, and the printing performance is adversely affected. Effect.
The number average primary particle size of the inorganic fine particles A is preferably 40 to 150 nm, and more preferably 45 to 100 nm.

  Examples of the inorganic fine particles A include inorganic fine particles made of silica, titanium oxide, aluminum oxide, tin oxide, calcium carbonate, calcium phosphate, cerium oxide, a mixture of these inorganic substances, or the like. Among these, silica fine particles and titanium oxide fine particles are preferable, silica fine particles are more preferable, and colloidal silica fine particles are more preferable.

The amount of adsorbed moisture of the inorganic fine particles A is preferably 0.1 to 0.4% by mass, and 0.2 to 0.3% by mass when the total mass of the inorganic fine particles A is 100% by mass. Is more preferable. If the amount of adsorbed moisture of the inorganic fine particles A exceeds the above range, there is a possibility that the chargeability is lowered or filming on the photoreceptor is caused.
The amount of adsorbed moisture of the inorganic fine particles A can be measured by an adsorption / desorption measurement device, a continuous vapor adsorption device, or the like.

The content of the inorganic fine particles A is usually 0.2 to 3.0 parts by weight, preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the colored resin particles, and 0.7 to More preferably, it is 1.5 parts by mass.
When the content of the inorganic fine particles A is less than 0.2 parts by mass, the function as an external additive cannot be sufficiently exhibited, and the printing performance is adversely affected. On the other hand, when the content of the inorganic fine particles A exceeds 3.0 parts by mass, the inorganic fine particles A are easily released from the surface of the toner particles, the function as an external additive is lowered, and the printing performance is adversely affected. Effect.

In the present invention, inorganic fine particles B having a number average primary particle size of 11 to 30 nm are contained as an external additive. When the number average primary particle size of the inorganic fine particles B is less than 11 nm, the inorganic fine particles B are easily embedded from the surface to the inside of the colored resin particles, and when the number of printed sheets is large, the toner particles have sufficient fluidity. Can not be imparted to the printing performance, adversely affecting printing performance. On the other hand, when the number average primary particle size of the inorganic fine particles B exceeds 30 nm, the ratio (coverage) of the inorganic fine particles B to the surface of the toner particles is reduced, so that the toner particles have sufficient fluidity. Cannot be granted.
The number average primary particle size of the inorganic fine particles B is preferably 13 to 25 nm, and more preferably 15 to 20 nm.

  Examples of the inorganic fine particles B include inorganic fine particles made of silica, titanium oxide, aluminum oxide, tin oxide, calcium carbonate, calcium phosphate, cerium oxide, a mixture of these inorganic substances, or the like. Among these, silica fine particles and titanium oxide fine particles are preferable, and silica fine particles are more preferable.

The amount of moisture adsorbed by the inorganic fine particles B is preferably 0.1 to 0.6% by mass, and preferably 0.2 to 0.5% by mass, when the total mass of the inorganic fine particles B is 100% by mass. Is more preferable. If the amount of adsorbed moisture of the inorganic fine particles B exceeds the above range, there is a possibility that the chargeability is lowered or filming on the photoreceptor is caused.
The method for measuring the amount of adsorbed moisture of the inorganic fine particles B is the same as the amount of adsorbed moisture of the inorganic fine particles A.

The content of the inorganic fine particles B is usually 0.1 to 2.0 parts by weight, preferably 0.3 to 1.2 parts by weight, with respect to 100 parts by weight of the colored resin particles. It is more preferable that it is 0.8 mass part.
When the content of the inorganic fine particles B is less than 0.1 parts by mass, the function as the external additive cannot be sufficiently exhibited, and the fluidity is lowered, and the storage stability and durability are lowered. On the other hand, when the content of the inorganic fine particles B exceeds 2.0 parts by mass, the inorganic fine particles B are easily released from the surface of the toner particles, and the chargeability in a high-temperature and high-humidity environment is lowered and fogging occurs. To do.

In the present invention, inorganic fine particles C having a number average primary particle size of 5 to 10 nm are contained as an external additive. When the number average primary particle size of the inorganic fine particles C is less than 5 nm, the inorganic fine particles C are easily embedded from the surface to the inside of the colored resin particles, and sufficient fluidity can be imparted to the toner particles. The printing performance may be adversely affected. On the other hand, when the number average primary particle size of the inorganic fine particles C exceeds 10 nm, the proportion (coverage) of the inorganic fine particles C with respect to the surface of the toner particles is reduced, so that the toner particles have sufficient fluidity. May not be granted.
The number average primary particle size of the inorganic fine particles C is more preferably 6.5 to 9 nm, and further preferably 7 to 8 nm.

The amount of adsorbed moisture of the inorganic fine particles C is preferably 0.1 to 1.0% by mass, and 0.2 to 0.8% by mass when the total mass of the inorganic fine particles C is 100% by mass. Is more preferable. When the adsorbed moisture content of the inorganic fine particles C exceeds the above range, there is a possibility that the chargeability may be lowered or filming on the photoreceptor may be caused.
The method for measuring the amount of adsorbed moisture of the inorganic fine particles C is the same as the amount of adsorbed moisture of the inorganic fine particles A.

The content of the inorganic fine particles C is usually 0.1 to 1.0 part by weight, preferably 0.2 to 0.8 part by weight, based on 100 parts by weight of the colored resin particles. More preferably, it is 0.7 parts by mass.
When the content of the inorganic fine particles C is less than 0.1 part by mass, the function as the external additive cannot be sufficiently exhibited, and the fluidity is lowered or the storage stability is lowered. On the other hand, when the content of the inorganic fine particles C exceeds 1.0 part by mass, the inorganic fine particles C are easily released from the surface of the toner particles, and the chargeability in a high-temperature and high-humidity environment is reduced and fogging occurs. To do.

  The inorganic fine particles A, inorganic fine particles B, and inorganic fine particles C used in the present invention are preferably surface-treated with a hydrophobic treatment agent having a positively chargeable functional group. In the surface treatment of these three kinds of inorganic fine particles, in order to adjust the hydrophobicity and / or the positive chargeability, a general hydrophobic treatment agent having no chargeable group can be used in combination. These three kinds of inorganic fine particles are preferably hydrophobized with a silicon compound, and more preferably hydrophobized with two or more silicon compounds. When hydrophobizing using two or more silicon compounds, in order to impart high positive chargeability, at least one of the two or more silicon compounds is a silicon compound containing an amino group, The other silicon compound is preferably a silicon compound containing no amino group.

  As the silicon compound containing an amino group, various compounds can be used without being limited to specific ones. For example, an amino group-containing silane coupling agent, an amino-modified silicone oil, a quaternary ammonium salt type silane, Cyclic silazane and the like can be used. Among these, amino group-containing silane coupling is particularly preferable from the viewpoint of positive charge imparting ability and fluidity. Specific examples of the amino group-containing silane coupling agent include, for example, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, and the like can be mentioned. Among them, the effect of improving the environmental stability of charging performance is excellent, which is preferable. Is preferably a coupling agent having an aminoalkyl group.

  As the silicon compound not containing an amino group, various compounds can be used without any particular limitation as long as they do not contain an amino group and express hydrophobicity. However, environmental stability and fluidity of charging performance can be used. From this point of view, for example, alkoxysilane, silane coupling agent, silazane, silicone oil, silicone resin, and the like are preferable, and alkoxysilane, silicone oil, and silicone resin are particularly preferable. Examples of the alkoxysilane include isobutyltrimethoxysilane, octyltriethoxysilane, and trifluoropropyltrimethoxysilane. Examples of the silicone oil include straight silicone oils such as dimethylpolysiloxane and methylhydrogenpolysiloxane. And modified silicone oils such as epoxy-modified silicone oil and fluorine-modified silicone oil. Examples of the silicone resin include trimethylsiloxysilicic acid.

  As the inorganic fine particles A, various commercially available products can be used. For example, VPNA50H (: trade name, number average primary particle size: 40 nm), NA50Y (: trade name, number average primary particle size: manufactured by Nippon Aerosil Co., Ltd .: 35 nm); HDK H05TA (: trade name, number average primary particle size: 50 nm), HDK H05TX (: trade name, number average primary particle size: 50 nm); TG-C321 (: trade name) manufactured by Cabot Corporation , Number average primary particle size: 70 nm);

  Various commercially available products can be used as the inorganic fine particles B. For example, HDK2150 (: trade name, number average primary particle size: 12 nm) manufactured by Clariant, NA130Y (: trade name, number average, manufactured by Nippon Aerosil Co., Ltd.) Primary particle size: 20 nm), R504 (: product name, number average primary particle size: 12 nm), RA200HS (: product name, number average primary particle size: 12 nm); MSP-012 (: product name, number) Average primary particle size: 16 nm), MSP-013 (: trade name, number average primary particle size: 12 nm); TG-7120 manufactured by Cabot Corporation (: trade name, number average primary particle size: 20 nm), and the like.

  As the inorganic fine particles C, various commercially available products can be used. For example, TG820F manufactured by Cabot Corporation (: trade name, number average primary particle size: 7 nm); RY300 manufactured by Nippon Aerosil Co., Ltd. (: trade name, number average) Primary particle size: 7 nm).

In the present invention, the total content of inorganic fine particles A, inorganic fine particles B, and inorganic fine particles C (hereinafter sometimes referred to as the total content of inorganic fine particles) is 1.2 relative to 100 parts by mass of the colored resin particles. It is preferably ˜4.0 parts by mass. If the total content of the inorganic fine particles is less than 1.2 parts by mass, there is a possibility that transfer residue may occur. If the total content of the inorganic fine particles exceeds 4.0 parts by mass, fog may occur.
The total content of the inorganic fine particles is more preferably 1.5 to 3.5 parts by mass, and more preferably 2.0 to 3.0 parts by mass with respect to 100 parts by mass of the colored resin particles.

In the present invention, it is preferable to further contain fatty acid metal salt particles having a number average primary particle size of 100 to 2,000 nm as an external additive. When the number average primary particle size of the fatty acid metal salt particles is less than 100 nm, the chargeability of the toner may be reduced and fogging may occur. On the other hand, when the number average primary particle size of the fatty acid metal salt fine particles exceeds 2,000 nm, white spots may occur in the printed image.
The number average primary particle size of the fatty acid metal salt fine particles is preferably 500 to 1,500 nm, and more preferably 800 to 1,000 nm.

  Examples of the metal constituting the fatty acid metal salt include Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Zn and the like.

Fatty site of fatty acid metal salt (R-COO ^-) and the corresponding fatty acids (R-COOH), out of a carboxylic acid (R-COOH) having a carboxyl group (-COOH), a all that with a chain structure Including. In the present invention, the fatty acid moiety is preferably derived from a higher fatty acid having a large number of carbon atoms in the alkyl group (R-).

Examples of the higher fatty acid (R—COOH) include lauric acid (CH ₃ (CH ₂ ) ₁₀ COOH), tridecanoic acid (CH ₃ (CH ₂ ) ₁₁ COOH), and myristic acid (CH ₃ (CH ₂ ) ₁₂ COOH). ), Pentadecanoic acid (CH ₃ (CH ₂ ) ₁₃ COOH), palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH), heptadecanoic acid (CH ₃ (CH ₂ ) ₁₅ COOH), stearic acid (CH ₃ (CH ₂ )) ₁₆ COOH), arachidic acid (CH ₃ (CH ₂ ) ₁₈ COOH), behenic acid (CH ₃ (CH ₂ ) ₂₀ COOH), and lignoceric acid (CH ₃ (CH ₂ ) ₂₂ COOH).

  Specific examples of the fatty acid metal salt include lithium laurate, sodium laurate, potassium laurate, magnesium laurate, calcium laurate, barium laurate and the like; lithium myristate, sodium myristate, potassium myristate Metal myristate such as magnesium myristate, calcium myristate, barium myristate; metal palmitate such as lithium palmitate, sodium palmitate, potassium palmitate, magnesium palmitate, calcium palmitate, barium palmitate; stearin Lithium oxide, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate, etc. Stearic acid metal salts; and the like typically stearic acid metal salts are preferred. Among them, zinc stearate is more preferred.

  The fatty acid metal salt fine particles suitably used as an external additive in the present invention are preferably used in an amount of 0.01 to 1 part by weight, more preferably 0.03 to 0.3 part by weight, based on 100 parts by weight of the colored resin particles. Used part.

  Various commercially available products can be used as the fatty acid metal salt particles. For example, SPL-100F (: trade name, lithium stearate, number average primary particle size: 0.71 μm), SPX- 100F (: trade name, magnesium stearate, number average primary particle size: 0.72 μm), SPC-100F (: trade name, calcium stearate, number average primary particle size: 0.51 μm), SPZ-100F (: trade name) Zinc stearate, number average primary particle size: 0.5 μm) and the like.

4). Toner of the present invention The toner obtained through the above steps has excellent fixability even in high-speed printing, no blurring occurs at the beginning and after durability, excellent printing durability and fine line reproducibility, and good storage stability. Toner.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited only to these examples. Parts and% are based on mass unless otherwise specified.
The test methods performed in the examples and comparative examples are as follows.

1. Production of toner [Example 1]
75 parts of styrene and 25 parts of n-butyl acrylate as a polymerizable monomer and 7 parts of carbon black (manufactured by Mitsubishi Chemical Corporation, trade name: # 25B) as a black colorant, a disperser (manufactured by Shinmaru Enterprises, product) Name: Dynomill) was used to obtain a polymerizable monomer mixture.
In the polymerizable monomer mixture, 0.70 part of charge control resin (manufactured by Fujikura Kasei Co., Ltd., quaternary ammonium base-containing styrene acrylic resin) as a charge control agent, and polyfunctional ester wax (manufactured by NOF Corporation) as a release agent Trade name: WEP7) 5 parts, paraffin wax (manufactured by Nippon Seiwa Co., Ltd., trade name: HNP-11), 5 parts, polymethacrylic acid ester macromonomer as macromonomer (trade name: AA6) 0 .3 parts, 0.6 parts of divinylbenzene as a crosslinkable polymerizable monomer, and 1.5 parts of t-dodecyl mercaptan as a molecular weight regulator are added, mixed and dissolved to obtain a polymerizable monomer composition. Was prepared.

On the other hand, at room temperature, in an aqueous solution in which 10.2 parts of magnesium chloride (water-soluble polyvalent metal salt) is dissolved in 250 parts of ion-exchanged water, sodium hydroxide (alkali metal hydroxide) 6.2 in 50 parts of ion-exchanged water. The aqueous solution in which the part was dissolved was gradually added with stirring to prepare a magnesium hydroxide colloid (slightly water-soluble metal hydroxide colloid) dispersion.
The polymerizable monomer composition was charged into the magnesium hydroxide colloid dispersion at room temperature and stirred. After 4.4 parts of the polymerization initiator was added thereto, dispersion was performed by high-speed shearing stirring for 10 minutes at a rotational speed of 15,000 rpm using an in-line type emulsifying disperser (trade name: Milder, manufactured by Taiheiyo Kiko Co., Ltd.). And droplet formation of the polymerizable monomer composition was performed.

A suspension (polymerizable monomer composition dispersion) in which droplets of the polymerizable monomer composition are dispersed is placed in a reactor equipped with a stirring blade, heated to 90 ° C., and polymerized. The reaction was started. When the polymerization conversion reached almost 100%, 2,2′-azobis (shell polymerization initiator dissolved in 1 part of methyl methacrylate and 10 parts of ion-exchanged water as shell polymerizable monomer) 0.3 part of 2-methyl-N- (2-hydroxyethyl) -propionamide) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble) was added, and the reaction was continued at 90 ° C. for 4 hours. Thereafter, the reaction was stopped by cooling with water to obtain an aqueous dispersion of colored resin particles having a core-shell structure.
While stirring the aqueous dispersion of the colored resin particles, sulfuric acid was added dropwise at room temperature, and acid washing was performed until the pH was 6.5 or lower. Subsequently, filtration separation was performed, 500 parts of ion-exchanged water was added to the obtained solid content to make a slurry again, and water washing treatment (washing, filtration, and dehydration) was repeated several times. Subsequently, filtration separation was performed, the obtained solid content was put in a container of a dryer, and dried at 40 ° C. for 24 hours to obtain dried colored resin particles. The obtained colored resin particles have a volume average particle size (Dv) of 8.1 μm, a number average particle size (Dn) of 7.3 μm, a particle size distribution (Dv / Dn) of 1.11. It was 0.986.

  To 100 parts of the colored resin particles obtained above, melamine / formaldehyde condensate particles having a number average primary particle size of 100 nm as nitrogen-containing resin particles as external additives (made by Nippon Shokubai Co., Ltd., trade name: Eposter SS, hereinafter Particle 1) 0.5 parts, silica fine particles having a number average primary particle size of 50 nm as inorganic fine particles A (manufactured by Wacker, trade name: HDK H05TA, adsorbed water content: 0.3 mass%) 1.0 part, Silica fine particles having a number average primary particle size of 20 nm as inorganic fine particles B (manufactured by Nippon Aerosil Co., Ltd., trade name: NA130Y, amount of adsorbed water: 0.2% by mass), 0.6 parts of inorganic fine particles C having a number average primary particle size of 7 nm 0.4 parts of silica fine particles (manufactured by Cabot, trade name: TG820F, adsorbed water content: 0.7 mass%), and stearic acid sub-oxide having a number average primary particle size of 500 nm A 10-L lab with 0.2 parts of particles (manufactured by Sakai Chemical Co., Ltd., trade name: SPZ-100F, adsorbed water content: 0.1% by mass, hereinafter may be referred to as particles d) and having a cooling jacket Using a high-speed stirrer (trade name: FM mixer, manufactured by Nippon Coke Kogyo Co., Ltd.), the mixture was stirred and agitated at a peripheral speed of a stirring blade of 40 m / second and an external treatment time of 300 seconds, and the toner was added. Obtained. The evaluation results are shown in Table 1.

[Example 2 to Example 10, Comparative Example 1 to Comparative Example 9]
A toner was obtained in the same manner as in Example 1 except that the type of the colored resin particles or the amount of the external additive added was changed as shown in Tables 1 and 2 below. The evaluation results are shown in Table 1. The colored resin particles used in Comparative Example 2 were prepared by adding the charge control resin (Fujikura Kasei Co., Ltd., quaternary ammonium base-containing styrene acrylic resin) in the colored resin particle manufacturing method described in Example 1 above. The same production method was used except that the content was changed from 0.70 parts to 2.00 parts.

[Comparative Example 10]
In Example 2, 0.5 part of melamine / formaldehyde condensate particles having a number average primary particle size of 100 nm (manufactured by Nippon Shokubai Co., Ltd., trade name: Eposta SS, Particle 1) were mixed with melamine / formaldehyde condensation having a number average primary particle size of 200 nm. A toner was obtained in the same manner as in Example 2 except that the amount was changed to 0.5 part of product particles (manufactured by Nippon Shokubai Co., Ltd., trade name: Eposter S, sometimes referred to as Particle 2). The evaluation results are shown in Table 1.

2. Characteristic Evaluation of Colored Resin Particles and Toner Properties of the toners of Examples 1 to 10 and Comparative Examples 1 to 10 and the colored resin particles used in these toners were examined. Details are as follows.

(1) Particle size measurement of colored resin particles Volume average primary particle size Dv, number average primary particle size Dn, and particle size distribution Dv / Dn of colored resin particles are measured by a particle size measuring machine (Beckman Coulter, product name: Measured by Multisizer). The measurement with this multisizer was performed under the conditions of an aperture diameter: 100 μm, a dispersion medium: Isoton II (trade name), a concentration of 10%, and a measurement particle number: 100,000.
Specifically, 0.2 g of a colored resin particle sample was placed in a beaker, and an alkylbenzenesulfonic acid aqueous solution (manufactured by Fuji Film Co., Ltd., trade name: Drywell) was added as a dispersant therein. Further, 2 mL of a dispersion medium was added to wet the colored resin particles, 10 mL of the dispersion medium was added, and the mixture was dispersed with an ultrasonic disperser for 1 minute, and then measured with the particle size measuring instrument.

(2) Average circularity Into a container, 10 mL of ion exchange water is put in advance, 0.02 g of a surfactant (alkylbenzenesulfonic acid) is added as a dispersant, and 0.02 g of a measurement sample (colored resin particles) is further added. In addition, 60 W (Watt) was applied for 3 minutes with an ultrasonic disperser. The concentration of the colored resin particles at the time of measurement is adjusted to 3,000 to 10,000 particles / μL, and 1,000 to 10,000 colored resin particles having an equivalent circle diameter of 0.4 μm or more are flow-type particle images. Measurement was performed using an analyzer (trade name: FPIA-2100, manufactured by Simex Corporation). The average circularity was determined from the measured value.
The circularity is shown in the following calculation formula 1, and the average circularity is an average of the circularity.
Formula 1: (Circularity) = (Perimeter of circle equal to projected area of particle) / (Perimeter of projected image of particle)

(3) Preservability 10 g of the toner was put in a sealable container (made of polyethylene, capacity 100 mL) and sealed, and then the container was submerged in a constant temperature water bath maintained at a temperature of 55 ° C. After 8 hours, the container was taken out from the thermostatic water bath, and the toner in the container was placed on a 42 mesh sieve. At this time, the toner was gently taken out of the container and carefully transferred onto a sieve so as not to destroy the toner aggregation structure in the container. The sieve on which the toner was placed was vibrated for 30 seconds under a condition of an amplitude of 1 mm using a powder measuring machine (manufactured by Hosokawa Micron Corporation, trade name: Powder Tester PT-R), and the mass of the toner remaining on the sieve was measured. Measurement was made to be the mass of the aggregated toner. The ratio (mass%) of the mass of the aggregated toner to the mass of the toner initially put in the container was calculated. The above measurement was performed three times for each sample, the mass ratio (mass%) of the aggregated toner was calculated, and the average value was used as an index of storage stability.

3. Printing evaluation of toner Printing evaluation was performed on the toners of Examples 1 to 10 and Comparative Examples 1 to 10. Details are as follows.
(1) Minimum Fixing Temperature A fixing test was conducted using a printer modified so that the temperature of the fixing roll part of a commercially available non-magnetic one-component developing type printer could be changed. In the fixing test, black solid (printing density 100%) is printed, the temperature of the fixing roll of the modified printer is changed by 5 ° C., and the toner fixing rate at each temperature is measured. I went for a relationship. The fixing rate was calculated from the ratio of image density before and after the tape was peeled off in the black solid (printing density 100%) printing area. That is, if the image density before tape peeling is ID (front) and the image density after tape peeling is ID (back), the fixing ratio can be calculated by the following calculation formula 2.
Formula 2: Fixing rate (%) = (ID (rear) / ID (front)) × 100

  The tape peeling operation means that an adhesive tape (manufactured by Sumitomo 3M Co., Ltd., trade name: Scotch Mending Tape 810-3-18) is applied to the measurement part of the test paper, and is attached by pressing at a constant pressure, and then at a constant speed It is a series of operations for peeling the adhesive tape in the direction along the paper. The image density was measured using a reflection type image densitometer (manufactured by Macbeth, trade name: RD914). In this fixing test, the lowest fixing roll temperature at which the fixing rate exceeds 80% was defined as the minimum fixing temperature of the toner.

(2) Printing durability Set printing paper in the above-mentioned printer, put toner in the developing device, leave it in a normal temperature and normal humidity (N / N) environment at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. Continuous printing was performed at 5% printing density under the environment. Solid printing (printing density 100%) is performed every 500 sheets, and a three-point printing density at the center of a black solid image is measured using a reflection type image densitometer (trade name: RD918, manufactured by Macbeth Co.). Is the print density.
Further, after that, white solid printing (print density 0%) is performed, the printer is stopped in the middle of white solid printing, and the toner in the non-image area on the photoconductor after development is adhered to an adhesive tape (Sumitomo 3M, Product name: Scotch mending tape 810-3-18), and then peeled off and affixed to printing paper. Next, the whiteness (B) of the printing paper on which the adhesive tape is affixed is measured with a whiteness meter (trade name: ND-1 manufactured by Nippon Denshoku Co., Ltd.). The whiteness (A) was measured and the whiteness difference (B−A) was defined as the fog value.
The number of continuous prints that can maintain the image quality in which the print density when performing the above solid printing is 1.3 or more and the fog value when performing the white solid printing is 1 or less was tested up to 15,000 sheets. Note that “15000 <” in the test results of Tables 1 and 2 indicates that the above-mentioned criteria are satisfied even when printing 15,000 sheets continuously.

(3) Initial Scratch and Durability Durability In addition to the evaluation in (2) above, evaluation of initial scum and post-durability scum was also performed.
For the initial blur, in the solid black printed material after printing 500 sheets in the endurance printability test, the print density was measured at each of three points, the black solid image upper part and the black solid image lower part. The difference between the upper print density and the lower print density was calculated as the print density, and used as an index of blur.
Scratch after endurance is evaluated in the same manner as initial scoring when the above test is completed with 15,000 continuous prints or when the above test is interrupted with less than 15,000 continuous prints due to poor durability. Carried out.

(4) Fine line reproducibility In the fine line reproducibility test, the above-described commercially available non-magnetic one-component development type printer (printing speed: A4 size 24 sheets / min) was used. Toner of this printer is put in the developing device of this printer, copy paper is set, and it is left overnight in a low temperature and low humidity (L / L) environment at a temperature of 10 ° C. and a humidity of 20% RH. Line images were continuously formed at a width of about 85 μm, and each 500 sheets were measured by a print evaluation system (trade name: RT2000, manufactured by YA-MA), and density distribution data of the line image was collected. At this time, with the full width at the half maximum of the density as the line width and the line width of the first line image as a reference, if the difference in the line width is 10 μm or less, the first line image is reproduced. The number of sheets that can maintain the line width difference of 10 μm or less was examined up to 10,000 sheets.
The test results in Tables 1 and 2 indicate that “10000 <”, the line image satisfying the above criteria can be maintained even when the fine line reproducibility test is performed up to 10,000 sheets, and the fine line reproducibility is good. It shows that it was.

(5) Initial fog test Set printing paper in a commercially available non-magnetic one-component developing system printer (printing speed: 28 sheets / min), put toner in the developing device, and high temperature and high humidity at 35 ° C and humidity 80% RH. After being left in a (H / H) environment for 24 hours, three sheets were continuously printed at a printing density of 5% in the same environment.
After that, white solid printing (printing density 0%) is performed, the printer is stopped in the middle of white solid printing, and the toner in the non-image area on the developed photosensitive member is adhesive tape (product name: manufactured by Sumitomo 3M Limited). The scotch mending tape 810-3-18) was attached to the printing paper. Next, the whiteness (B) of the printing paper with the adhesive tape attached is measured with a whiteness meter (Nippon Denshoku Co., Ltd.), and in the same way, only the unused adhesive tape is attached to the printing paper. The whiteness (A) was measured, and the difference in whiteness (B−A) was defined as the fog value. The smaller the fog value, the less the fog and the better.

  Tables 1 and 2 show the measurement and evaluation results of the toners of Examples 1 to 10 and Comparative Examples 1 to 10. In Table 1 and Table 2 below, “HH fog” means a fog value in a high temperature and high humidity (H / H) environment in the initial fog test.

4). Summary of Toner Evaluation Hereinafter, the toner evaluation will be examined with reference to Tables 1 and 2.
First, the toners of Comparative Example 1 and Comparative Example 6 are examined. From Table 2, the toner of Comparative Example 1 shows no particular problem with respect to storage stability, fixing property, initial blur, and post-durability blur. However, the toner of Comparative Example 1 has a small print durability evaluation number of 7,000, a fine line reproducibility evaluation number of 5,000, and an HH fog value of 2.2. In particular, the number of print durability evaluated is the smallest among the toners measured this time.
On the other hand, the toner of Comparative Example 6 has no particular problem with respect to storage stability, printing durability, and fine line reproducibility. However, the toner of Comparative Example 6 has a minimum fixing temperature as high as 165 ° C. The toner of Comparative Example 6 had a large ID difference of 0.35 in the initial blur evaluation, and could not be measured until the ID in the post-endurance blur evaluation. The ID difference in the initial blur evaluation is the largest among the toners measured this time. Further, the toner of Comparative Example 6 has a high HH fog value of 4.3.
From the above, it can be seen that the toner of Comparative Example 1 containing no nitrogen-containing resin particles is particularly poor in printing durability, inferior in fine line reproducibility, and more likely to cause fogging. On the other hand, the toner of Comparative Example 6 containing more than 1.5 parts by mass of the nitrogen-containing resin particles with respect to 100 parts by mass of the colored resin particles is inferior in fixability and generally tends to cause blurring in addition to fogging. I understand.

As shown in Table 2, the toner of Comparative Example 2 has the same toner composition as that of Comparative Example 1 except that the type of the colored resin particles is different. As compared with the toner of Comparative Example 1, the toner of Comparative Example 2 has an improved print durability evaluation number of 13,000 sheets and an HH fog value of 0.6, which is within the allowable range. However, in the toner of Comparative Example 2, the evaluation number of fine line reproducibility is as small as 4,000, which is further worse than that of Comparative Example 1.
From the above, it is not sufficient to change the composition of the colored resin particles in order to improve at least the printing durability and fine line reproducibility and to suppress the occurrence of initial fogging in a high temperature and high humidity (H / H) environment as much as possible. I understand that.

Next, the toners of Comparative Example 3 and Comparative Example 7 will be examined. From Table 2, the toner of Comparative Example 3 shows no particular problem in the fixing property, initial blurring, and fine line reproducibility. However, the toner of Comparative Example 3 has a large blocking amount of 10.5 g. This value is the largest blocking amount value among the toners measured this time. In addition, the toner of Comparative Example 3 has a small print durability evaluation number of 9,000 sheets, an ID difference in post-endurance evaluation is as large as 0.25, and a HH fog value is as high as 3.1.
On the other hand, the toner of Comparative Example 7 has no particular problem with respect to storage stability, printing durability, initial blurring, and fine line reproducibility. However, the toner of Comparative Example 7 has a minimum fixing temperature as high as 170 ° C. In addition, the toner of Comparative Example 7 has a large ID difference of 0.15 in evaluation of blur after durability.
From the above, it can be seen that the toner of Comparative Example 3 that does not contain inorganic fine particles A has poor storage stability and printing durability, tends to cause blurring after long-time printing, and further tends to cause fogging in a high-temperature and high-humidity environment. This is because, when an external additive having a relatively large particle size is not included like the inorganic fine particles A, the inorganic fine particles B having a smaller particle size cannot be prevented from being embedded in the colored resin particles. Indicates that the durability is low. On the other hand, the toner of Comparative Example 7 containing inorganic fine particles A exceeding 3.0 parts by mass with respect to 100 parts by mass of the colored resin particles is improved in terms of storage stability, printing durability, and generation of HH fogging. It can be seen that there is no improvement in blurring after printing for a long time.

Subsequently, the toners of Comparative Example 4 and Comparative Example 8 will be examined. From Table 2, the toner of Comparative Example 4 shows no particular problems in storage stability, fixability, initial blurring, and fine line reproducibility. However, the toner of Comparative Example 4 has a small print durability evaluation number of 10,000, and the ID difference in the post-end wear evaluation is as large as 0.15. Further, the toner of Comparative Example 4 has a high HH fog value of 8.1. This value is the highest HH fog value among the toners measured this time.
On the other hand, the toner of Comparative Example 8 has no particular problem with respect to storage stability, printing durability, initial blur, and HH fog. However, the toner of Comparative Example 8 has a minimum fixing temperature as high as 175 ° C. This value is the highest minimum fixing temperature among the toners measured this time. Further, the toner of Comparative Example 8 did not satisfy the above-mentioned standard for fine line reproducibility from the beginning of printing.
From the above, it can be seen that the toner of Comparative Example 4 that does not contain the inorganic fine particles B is poor in printing durability, so that it is likely to cause blurring after long-time printing, and fogging is likely to occur in a high-temperature and high-humidity environment. This indicates that when an external additive having a relatively small particle size is not included as in the case of the inorganic fine particles B, the fluidity is lost from the toner. . On the other hand, the toner of Comparative Example 8 containing inorganic fine particles B in excess of 2.0 parts by mass with respect to 100 parts by mass of the colored resin particles is improved in terms of printing durability and occurrence of HH fogging, but fixing properties and fine lines are improved. It can be seen that the reproducibility is particularly deteriorated and no improvement is observed with respect to the blur after long-time printing.

Next, the toners of Comparative Example 5 and Comparative Example 9 will be examined. From Table 2, the toner of Comparative Example 5 does not have any particular problems with storage stability, fixing performance, printing durability, fine line reproducibility, and HH fog. However, the toner of Comparative Example 5 has a large ID difference of 0.22 in the initial blur evaluation and a large ID difference of 0.26 in the post-endurance blur evaluation.
On the other hand, the toner of Comparative Example 9 has no particular problem with respect to storage stability, initial blurring, fine line reproducibility, and HH fog. However, the toner of Comparative Example 9 has a minimum fixing temperature as high as 170 ° C., and the print durability evaluation number is as low as 9,000.
From the above, it can be seen that the toner of Comparative Example 5 that does not contain the inorganic fine particles C generally tends to be blurred. This indicates that when the external additive having a relatively small particle size is not included as in the case of the inorganic fine particles B, the fluidity is lost from the toner, and as a result, the transfer state of the toner is deteriorated and the blur tends to occur. On the other hand, it can be seen that the toner of Comparative Example 9 containing inorganic fine particles C exceeding 1.0 part by mass with respect to 100 parts by mass of the colored resin particles is improved in terms of blurring but deteriorates in fixing property and printing durability. .

Subsequently, the toner of Comparative Example 10 will be examined. From Table 2, the toner of Comparative Example 10 shows no particular problem in storage stability, fixing performance, printing durability, fine line reproducibility, and HH fog. However, the toner of Comparative Example 10 had a large ID difference of 0.24 in the initial blur evaluation, and it was not possible to measure the ID in the post-endurance blur evaluation.
From the above, Comparative Example 10 using the particles 2 having a number average primary particle size of 200 nm instead of the particles 1 having a number average primary particle size of 100 nm as the nitrogen-containing resin particles generally tends to cause a blur. I understand. This is because, when nitrogen-containing resin particles having a number average primary particle size exceeding 150 nm are used as an external additive, the moisture-absorbing property of the nitrogen-containing resin particles becomes too high, so that the transfer state of the toner is deteriorated and blurring tends to occur. It shows that.

On the other hand, from Table 1, the toners of Examples 1 to 10 have a blocking amount as low as 0.9 g or less, a minimum fixing temperature as low as 160 ° C. or less, and an evaluation number of 11,000 sheets or more in evaluation of printing durability. The ID difference in the initial blur evaluation is as small as 0.10 or less, the ID difference in the blur evaluation after durability is as small as 0.13 or less, the evaluation number of fine line reproducibility is as large as 6,000 or more, and the HH fogging The value is as low as 1.5 or less.
Therefore, 0.2 to 1.0 parts by mass of nitrogen-containing resin particles having a number average primary particle size in the range of 10 to 150 nm, and 0.5% of inorganic fine particles A having a number average primary particle size in the range of 31 to 300 nm. -2.0 parts by mass, 0.3 to 1.2 parts by mass of inorganic fine particles B having a number average primary particle size of 11 to 30 nm, and inorganic fine particles having a number average primary particle size of 5 to 10 nm The toners of Examples 1 to 10 each containing 0.2 to 0.8 parts by mass of C are excellent in fixability even in high-speed printing, and are free from blurring even at the initial stage and after endurance, and printing durability. In addition, it can be seen that the fine line reproducibility is excellent and the storage stability is good.

Claims (5)

In the toner for electrostatic charge development containing the colored resin particles containing the binder resin and the colorant, and the external additive,
The external additive is based on 100 parts by mass of the colored resin particles.
0.05 to 1.5 parts by mass of nitrogen-containing resin particles having a number average primary particle size of 10 to 150 nm,
0.2 to 3.0 parts by mass of inorganic fine particles A having a number average primary particle size of 31 to 300 nm,
0.1 to 2.0 parts by mass of inorganic fine particles B having a number average primary particle size of 11 to 30 nm, and 0.1 to 1.0 parts by mass of inorganic fine particles C having a number average primary particle size of 5 to 10 nm,
An electrostatic charge image developing toner, comprising:   In the external additive, the adsorbed water amounts of the inorganic fine particles A, the inorganic fine particles B, and the inorganic fine particles C are 0.1 to 0.4 mass%, 0.1 to 0.6 mass%, and 0.1 to 1, respectively. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is 0.0 mass%.   In the external additive, the total content of the inorganic fine particles A, the inorganic fine particles B, and the inorganic fine particles C is 1.2 to 4.0 parts by mass with respect to 100 parts by mass of the colored resin particles. Item 3. The toner for developing an electrostatic charge image according to Item 1 or 2.   4. The electrostatic image developing toner according to claim 1, wherein the external additive further contains fatty acid metal salt particles having a number average primary particle size of 100 to 2,000 nm. .   In the external additive, the surface of each of the inorganic fine particles A, the inorganic fine particles B, and the inorganic fine particles C is treated with a hydrophobizing agent containing an amino group. Item 5. The toner for developing an electrostatic charge image according to any one of Items 1 to 4.