JP6288541B2 - Toner for dry electrostatic image development - Google Patents

Description

  The present invention relates to a dry electrostatic image developing toner used for image formation.

The toner used for image formation is required to have high chargeability. There is already a technology to make toner more highly charged by coating a resin with excellent chargeability on the outside of the toner main part, attaching resin fine particles, or adding a charge control agent to the toner main part. Are known.
However, the conventional toner has a problem that the charging performance is deteriorated (deteriorated) due to external factors and the passage of time.

For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2008-89918) provides a toner that sufficiently exhibits the function of a charge control agent, and also provides a toner manufacturing method that can manufacture the toner. For this purpose, it has a core region containing a resin component and a colorant, and an outer periphery of the core region, and a shell region having a composition different from that of the core region, and the charge control agent is dispersed in the shell. Thus, a configuration for improving the deterioration durability of the charging property is disclosed.
Although the charge control agent is dispersed in the shell, the shell area covers the outer periphery of the core area, and the external factors of the toner and the problem of deterioration (degradation) in charging performance over time are reduced to a lesser extent. It has not been solved basically.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2011-81258) discloses a polymerized toner excellent in chargeability, durability, and environmental stability and a method for producing the toner, a binder resin, a halogen A polymerized toner is disclosed in which a charge control agent having a halogen group is present on the surface of a toner main part containing a calixarene having a group. Although the charge control agent having a halogen group exists on the surface of the toner main part, there is no description that the toner surface forms a convex part, and although the chargeability deterioration at the time of saturation can be prevented, The problem of maintaining rising charging has not been solved fundamentally.

  The present invention is excellent in chargeability, and does not cause deterioration in charging performance (= toner deterioration) due to external factors or time. That is, the charging performance does not deteriorate in durability, and low temperature fixability, adhesion resistance, heat resistance An object of the present invention is to provide a toner for developing a dry electrostatic image having improved storage properties.

  In the dry electrostatic image developing toner containing at least a binder resin and a colorant, the present inventors have disclosed that the toner is composed of a main part and a convex part, and the convex part is formed on the surface of the main part. The average length of the long side of the convex portion is 0.1 μm or more and less than 0.5 μm, the standard deviation of the long side length of the convex portion is 0.2 or less, and the convex portion is covered. The problem can be solved by including at least a charge control agent and a resin in the material constituting the convex portion, and including at least one or more types of charge control agents in the toner main portion. The present invention was completed by finding out what can be done.

That is, the present invention relates to a dry electrostatic image developing toner as described below.
A toner for dry electrostatic charge image development having a sea-island structure with the main part of the toner as the sea and the convex part as an island,
The main part includes at least a binder resin, a colorant and a charge control agent ,
The charge control agent contained in the main part is unevenly distributed on the surface of the main part;
The convex portion includes at least a resin and a charge control agent,
The average length of the long side of the convex part is 0.1 μm or more and less than 0.5 μm,
The standard deviation of the length of the long side of the convex part is 0.2 or less,
A toner for developing a dry electrostatic charge image, wherein the coverage of the convex portions is 10% to 90%.

The toner for developing an electrostatic charge image of the present invention is provided with a uniform convex portion of a specific size on the surface of the toner main portion, and at least a charge control agent is contained in the convex portion, thereby allowing low temperature fixing property and anti-sticking property. The toner chargeability can be improved and high-quality image formation can be achieved while maintaining the heat-resistant storage property. Further, by including a charge control agent in the toner main part, even if the convex part arranged on the surface layer is peeled off or buried due to aging or external stress, it can exist as a highly charged toner. As a result, the new toner and the deteriorated toner can maintain the same level of charge.
Accordingly, it is possible to provide a toner in which the charging performance does not deteriorate due to external factors or the passage of time.

It is a figure explaining the measuring method of the coverage of the convex part of the toner in this invention. (A) It is sectional drawing of the toner in this invention. (B) It is sectional drawing of the deteriorated toner in this invention. 1 is a schematic cross-sectional view illustrating an example of a configuration of an image forming apparatus according to an embodiment of the present invention. It is a schematic sectional drawing which shows the structure of the image formation part which arrange | positions a photoreceptor. It is a schematic sectional drawing which shows the structure of a developing device. It is a schematic sectional drawing which shows an example of a structure of a process cartridge. It is a figure which shows the length of the long side of the convex part of the toner in this invention.

  An embodiment of the present invention will be described.

(Dry electrostatic charge image developing toner)
The dry electrostatic image developing toner of the present invention (hereinafter also referred to as toner)
A toner for dry electrostatic charge image development having a sea-island structure with the main part of the toner as the sea and the convex part as an island,
The main part includes at least a binder resin and a colorant, and the main part surface includes a charge control agent,
The convex portion includes at least a resin and a charge control agent,
The average length of the long side of the convex part is 0.1 μm or more and less than 0.5 μm,
The standard deviation of the length of the long side of the convex part is 0.2 or less,
The coverage of the convex portions is 10% to 90%.

As the toner of the present invention, a toner containing a binder resin, a colorant, and a charge control agent as essential components is used. The toner may contain an external additive, a release agent, or a plasticizer as necessary to assist fluidity, developability, and chargeability.
By using a toner with a convex portion made of the constituent resin of the dispersion and a charge control agent formed on the surface of the toner main part, the chargeability and heat-resistant storage stability are improved while maintaining low-temperature fixability, and the size of the convex portion is increased. By making the thickness uniform, it is possible to achieve high-quality image formation with uniform and stable chargeability and adhesion resistance.
As shown in FIG. 2A, the toner of the present invention is easily charged and has high chargeability because the convex portion of the toner contains a charge control agent. Even if the convex portion is damaged, peeled off or buried as shown in FIG. 2 (b) due to the toner deterioration accompanying the change with time, the charge control agent on the surface of the toner main part keeps the charge, so the charging performance does not deteriorate. Due to the formation of the protrusions, the specific surface area of the toner is increased and the toner is easily charged. By using a partial coating instead of a complete coating, the thermal properties of the binder resin are not impaired, and the toner fixing property and heat-resistant storage stability are not adversely affected. Charging performance can be obtained.

(Binder resin)
Examples of the binder resin include polyester, polyurethane, polyurea, epoxy resin, vinyl resin, and the like. Alternatively, a hybrid resin in which different resins are chemically bonded may be used. Further, a reactive functional group may be introduced into the terminal or side chain of the resin and may be extended by being bonded in the toner production process. Although one of these can be used alone, the binder resin constituting the toner main part is preferably different from the resin constituting the convex part in order to produce a toner having a convex part having a uniform size.

<Binder resin that constitutes toner main part>
As the binder resin constituting the toner main part, a resin that is at least partially dissolved in an organic solvent is used, but the acid value is preferably 2 to 24 mgKOH / g. When the acid value is 24 mgKOH / g or less, the transition to the aqueous phase is difficult to occur, and as a result, it is difficult for the material balance to be lost during the production process, or the dispersion stability of the oil droplets is deteriorated. The problem is less likely to occur. In addition, the toner has a low moisture adsorbing property, so that the charging ability is not easily lowered, and the storage property in a high temperature and high humidity environment is hardly deteriorated. On the other hand, when the acid value is 2 mgKOH / g or more, the polarity of the resin increases, so that a colorant having a certain degree of polarity can be uniformly dispersed in the oil droplets.

  The type of the resin is not particularly limited, but when used as an electrostatic image developing toner in electrophotography, it is preferable to use a resin having a polyester skeleton because good fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, and it is preferable to use a polyester resin because the uniformity of toner particles obtained is high.

Examples of the polyester resin include ring-opening polymers of lactones, polycondensation products of hydroxycarboxylic acids, polycondensates of polyols and polycarboxylic acids, and the like. Polycondensates are preferred.
The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When it is 1000 or more, heat-resistant storage stability is good, and when it is 30000 or less, low-temperature fixability is good as an electrostatic charge image developing toner.

  The glass transition temperature of the polyester resin is 45 to 70 ° C, preferably 50 to 65 ° C. When the main part is covered with a convex part as in the present invention, the resin in the convex part is plasticized by moisture in the atmosphere when stored in a high-temperature and high-humidity environment, which may cause a decrease in the glass transition temperature. During transportation of the toner or toner cartridge, a high-temperature and high-humidity environment of 40 ° C. and 90% is assumed, and the obtained toner particles are deformed when placed under a certain pressure, or the toner particles adhere to each other. 45 ° C. or higher is preferred because there is a possibility that the particles cannot behave. Moreover, when it is 70 degrees C or less, since low temperature fixability becomes favorable, it is preferable.

<Polyol>
Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2), (1-1) alone or (1-1) and a small amount of (1-2). Mixtures are preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.);
Alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.);
Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; 3,3′-difluoro-4,4′-dihydroxybiphenyl 4,4'-dihydroxybiphenyls such as bis (3-fluoro-4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2- Bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) ) -1,1,1,3,3,3-hexafluoropropyl Bis bread etc. (hydroxyphenyl) alkanes, bis (3-fluoro-4-hydroxyphenyl) bis (4-hydroxyphenyl) such as ethers ethers;
Examples thereof include alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.);
Trihydric or higher phenols (trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

<Polycarboxylic acid>
Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone or (2-1) and a small amount of ( The mixture of 2-2) is preferred.
Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.), 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid 5-trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2′-bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 3,3'-bis (trifluoromethyl Le) -4,4'-biphenyl dicarboxylic acid, 2,2'-bis (trifluoromethyl) -3,3'-biphenyl dicarboxylic acid, and the like hexafluoroisopropylidene diphthalic anhydride. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/2, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1.5, more preferably 1.3 / 1 to 1 / 1.3.

<Modified resin>
In addition, a modified resin having an isocyanate group at the terminal is dissolved in the oil phase for the purpose of increasing the mechanical strength of the obtained toner particles or preventing high temperature offset at the time of fixing in addition to the previous mechanical strength. Toner particles may be obtained. As a method for obtaining a modified resin, a method for obtaining a resin having an isocyanate group by polymerizing with an isocyanate-containing monomer, a method for obtaining a resin having an active hydrogen at the terminal, and then reacting with a polyisocyanate. Although the method of introduce | transducing an isocyanate group into a polymer terminal etc. is mentioned, The latter method can be preferably employ | adopted from the controllability of introducing an isocyanate group into a terminal. Examples of the active hydrogen include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferable. As the skeleton of the modified resin, in consideration of the uniformity of the particles, it is preferable to use the same resin as that dissolved in the organic solvent, and it is preferable to have a polyester skeleton. As a method for obtaining a resin having an alcoholic hydroxyl group at the end of the polyester, in the polycondensation of the polyol and the polycarboxylic acid, the polycondensation reaction may be carried out by making the number of functional groups of the polyol larger than the number of functional groups of the polycarboxylic acid. .

<Amine compound>
The isocyanate group of the modified resin is hydrolyzed in the process of dispersing the oil phase in the aqueous phase to obtain particles, and part of it becomes an amino group. The generated amino group reacts with the unreacted isocyanate group, and is elongated. The reaction proceeds. In addition to the above reaction, an amine compound can be used in combination for the purpose of reliably reacting the extension reaction or introducing a crosslinking point. As the amine compound (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and B1-B5 amino group blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); alicyclic diamines (4 , 4'-diamino-3,3'dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine) Etc.).
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.

Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  The ratio of amines (B) is such that the number of amino groups [NHx] in amines (B) is 4 times or less the number of isocyanate groups [NCO] in prepolymer (A) having an isocyanate group, preferably 2 It is not more than twice, more preferably not more than 1.5 times, and still more preferably not more than 1.2 times. If it exceeds 4 times, the excess amino group blocks the isocyanate and the extension reaction of the modified resin does not occur, so the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.

(Coloring agent)
As the colorant of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fayce Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.
The colorant may be used as a toner as long as it can produce a target color after fixing and does not impair fixing properties, storage properties, and granulation properties. The content of the colorant is desirably 7 to 9 parts by mass with respect to 100 parts by mass of toner for black, and about 5 to 8 parts by mass for other color toners. By making it within the predetermined amount, a desired color can be obtained, which is preferable from the viewpoint of granulation.

<Colorant masterbatch>
The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

<Master batch creation method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

(Charge control agent)
All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, calixarenes, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-108, E-304 (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.) of a quaternary ammonium salt molybdenum complex, quaternary ammonium salt Copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, boron complex LR-147 ( (Made by Nippon Carlit), copper phthalocyanine, perylene, quinacridone, azo Pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

The charge control agent contained in the convex portion is preferably a charge control agent having at least a ferrate skeleton. Ferrate skeleton has the chemical formula
And Rs may be the same or different.
It becomes easy to charge by using an unsaturated charge control agent for the convex portion.
The charge control agent having a phenolate skeleton is a calixarene having a phenol skeleton.

Further, as the charge control agent contained in the main part, calixarene is preferable, and halogenated calixarene is particularly preferable.
Halogenated calixarene is a generic name for compounds in which fluorine, chlorine, bromine, or iodine is contained in the calixarene molecule. These elements may be in a molecular chain or in an inclusion state. By containing a halogen element having a large electronegativity in the compound, more negative charge can be imparted.
The calixarene can be disposed on the toner surface layer and has high charging ability. In particular, a halogenated calixarene is preferable because of its high charging ability.

As the calixarene, all known ones can be used, including those in which the structural unit is a phenol derivative. Examples of the structural unit include derivatives such as phenol derivatives, resorcinol derivatives, pyrogallol derivatives, pyrrole derivatives, Heterocyclic five-membered aromatic compound derivatives such as thiol derivatives. Each of these is generally called calixarene, resorcinarene, pyrogallolarene, calic spirol, calixthiol, etc., but in the text, all these derivatives are collectively called calixarene. The structural unit of calixarene that can be used in the present invention is one or more combinations of the above derivative groups, and the structural unit is a paraffin chain such as methylene group, ethylene group, methoxy group, ethoxy group, methoxymethyl. A calixarene is formed by bridging at least one of an oxyparaffin chain containing an oxygen atom such as a group and a sulfur atom. Although there is no restriction | limiting in the number of structural units of calixarene, 4-16 are preferable from a dispersibility and a soluble viewpoint, Preferably 4-8 are good. The calixarene takes several conformations, but it doesn't matter whether it is corn or all alternates. Since it can be arranged on the surface layer of the toner and the charge control can be effectively performed, it is preferable to use calixarene among the charge control agents in addition to the toner main part. The charge control agent may be used in an amount in a range where the performance is exhibited and there is no hindrance to the fixing property, and is 0.5 to 5% by mass in the toner, preferably as a conversion in a state excluding the convex portion, It is good to contain 0.8-3 mass%.
The amount of the charge control agent in the convex portion is 0.01 to 5% by mass, preferably 0.1 to 2.5% by mass, and more preferably 0.15 to 2% by mass. When the content is 0.01% by mass or more, the effect of the charge control agent can be sufficiently exerted, and when the content is 5% by mass or less, the resin fine particles for convex portions can be easily manufactured.

  It is preferable as the charging property that a large amount of the charge control agent is unevenly distributed on the main surface layer. When the contour of the toner cross section overlaps the diagonal of a square with a side of 200 nm, the halogen concentration of the toner in the square is not less than 500 times and not more than 50000 times the halogen concentration in the 3 μm square on the side of the toner center. It is preferable that the charge control agent is appropriately concentrated on the main surface layer. When it is 500 times or more, effective charging can be performed. Moreover, when it is 50000 times or less, since it will be in the state by which the charge control agent was moderately concentrated in the surface layer, and it does not inhibit adhering a convex part to a main part, it is preferable.

(Release agent)
Further, the toner for developing a dry electrostatic image of the present invention may contain a release agent in the main part for the purpose of improving the fixing releasability. As the release agent, a material such as wax or silicone oil, which has a sufficiently low viscosity when heated in the fixing process and is difficult to dissolve or swell on the surface of the fixing member with other materials of toner particles is used. . Considering the storage stability of the toner particles themselves, it is preferable to use a wax that exists as a solid in the toner particles during normal storage.

Examples of waxes include long-chain hydrocarbons and carbonyl group-containing waxes. Examples of long-chain hydrocarbons include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); petroleum waxes (paraffin wax, sazol wax, microcrystalline wax, etc.) In addition to Fischer-Tropsch wax.
Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone).
Of these, long-chain hydrocarbons having particularly good releasability are preferred. Furthermore, when a long chain hydrocarbon is used as a release agent, a carbonyl group-containing wax may be used in combination. The release agent may be contained in the toner particles in an amount of 2 to 25% by mass, preferably 3 to 20% by mass, more preferably 4 to 15% by mass. When it is 2% by mass or more, the effect of improving the fixing releasability is exhibited, and when it is 25% by mass or less, the mechanical strength of the toner particles is increased.

(Fine particles for convex resin)
As the fine particles for convex resin in the present invention, those dispersed in an aqueous medium can be used. Examples of the resin constituting the fine particles for the convex resin include vinyl resins, polyesters, polyurethanes, polyureas, and epoxy resins. Of these, vinyl resins are preferred because the resin particles for convex portions dispersed in an aqueous medium can be easily obtained. As a method for obtaining an aqueous dispersion of vinyl-based convex resin fine particles, a known polymerization method such as an emulsion aggregation method, a suspension polymerization method, or a dispersion polymerization method may be used. Among these, an emulsion polymerization method is particularly preferable because particles having a particle size suitable for the present invention can be easily obtained.

(Fine particles for vinyl convex resin)
The vinyl convex resin fine particles used in the present invention are preferably vinyl resins obtained by polymerizing a monomer mixture comprising at least a styrene monomer, and the convex parts are composed of the vinyl resin and at least one charge control agent. It is preferable to have. As the charge control agent, all known ones can be used as well as the resin portion other than the fine particles for the convex resin.
In order to use the toner for developing an electrostatic charge image of the present invention as particles that function by charging, the surface of the toner particles should have a structure that is easy to be charged. A styrene monomer having an electron orbit that can stably exist in the monomer mixture is used in an amount of 50 to 95% by mass, preferably 80 to 95% by mass, more preferably 90 to 95% by mass. When the styrene monomer is 50% by mass or more, the chargeability of the obtained toner particles is improved. If it exceeds 95%, the affinity with the resin may deteriorate, so it is preferable to contain a slight amount of an acrylate ester.
Acrylic acid ester is a general term for compounds represented by the following chemical formula, and R represents an arbitrary substituent.

Here, the styrene monomer refers to an aromatic compound having a vinyl polymerizable functional group. Examples of the polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific examples of the styrene monomer include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene, and metal salts thereof. 4-styrenesulfonic acid or a metal salt thereof, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, and the like. Of these, it is preferable to mainly use styrene which is easily available, has excellent reactivity and high chargeability.

  In the vinyl resin used in the present invention, the acid monomer may be used in an amount of 0 to 7% by mass, preferably 0 to 4% by mass, more preferably 0 to 4% by mass of the monomer mixture. . When the acid monomer is used in excess of 7% by mass, the resulting vinyl-based convex resin fine particles have a high dispersion stability in itself, and thus such a dispersion in which oil droplets are dispersed in an aqueous phase is used. Even if vinyl-based convex resin fine particles are added, it is difficult to adhere at room temperature or is easily detached even if attached, and easily peels off during solvent removal, washing, drying, and external treatment . Furthermore, when the amount of the acid monomer used is 4% by mass or less, the change in chargeability can be reduced depending on the environment in which the obtained toner particles are used.

Here, the acid monomer means a compound having a vinyl polymerizable functional group and an acid group, and examples of the acid group include carboxylic acid, sulfonyl acid, and phosphonic acid.
Examples of the acid monomer include carboxyl group-containing vinyl monomers and salts thereof ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, itaconic acid mono Alkyl, itaconic acid glycol monoether, citraconic acid, monoalkyl citraconic acid, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, phosphate group-containing vinyl monomers and salts thereof, etc. There is. Of these, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate are preferred.

  On the other hand, an acrylate ester may be included to control the compatibility with the toner main part. Acrylic acid ester is a straight chain system such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, etc., a branched chain system such as isopropyl acrylate, and acrylic acid containing benzene rings such as benzyl acrylate and biphenyl acrylate. Esters may be used. These acrylic acid esters are desirably 1 to 30% by mass, preferably 5 to 25% by mass, and more preferably 10 to 20% by mass. It is preferable for the content to be 30% by mass or less because the heat-resistant storage property is improved. 1% by mass or more is preferable because the affinity with the main part is improved.

Although it does not specifically limit as a method of obtaining vinyl type convex resin fine particles, The following (a)-(f) is mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl-based convex resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resulting resin is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce convex resin fine particles.
(C) The resin mixture obtained by polymerizing the monomer mixture in advance and dissolving the obtained resin in a solvent is sprayed in the form of mist to produce convex resin fine particles.
(D) polymerizing the monomer mixture in advance and adding the solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in the solvent to precipitate convex resin fine particles; Next, the solvent is removed to produce convex resin fine particles.
(E) A monomer solution is polymerized in advance, and a resin solution obtained by dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the solvent is removed by heating or decompression.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.

Among these, the method (a) is preferable because it is easy to produce and the convex resin fine particles can be obtained as a dispersion, so that it can be smoothly applied to the next step.
In the method (a), when the polymerization reaction is performed, a dispersion stabilizer is added to the aqueous medium, or the dispersion stability of the convex resin fine particles formed by polymerization is added to the monomer that performs the polymerization reaction. It is preferable to add such a monomer (so-called reactive emulsifier) or use these two means in combination to impart dispersion stability of the resulting vinyl-based convex resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the resulting convex resin fine particles have low dispersion stability and are stored. It is poor in stability and aggregates during storage, or the dispersion stability of the particles in the convex resin fine particle adhesion process described later decreases, so the core particles tend to aggregate and coalesce, and finally obtained. This is not preferable because the uniformity of the particle size, shape, surface, etc. of the toner particles is deteriorated.

  Examples of the dispersion stabilizer include surfactants and inorganic dispersants. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamine salts. Amine salt types such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N Amphoteric surfactants such as N- dimethyl ammonium betaine and the like. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

  The weight average molecular weight of the vinyl resin is 3,000 to 300,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight is less than 3,000, the mechanical strength of the vinyl resin is weak and fragile, so the surface of the toner particles easily changes depending on the use state of the finally obtained toner particles. This is not preferable because it causes significant changes in properties, contamination such as adhesion to peripheral agents, and the accompanying quality problems. On the other hand, if it exceeds 300,000, the molecular ends are reduced, so that the entanglement of the molecular chain with the core particle is reduced and the adhesion to the core particle is lowered, which is not preferable.

  The glass transition temperature (Tg) of the vinyl resin is 45 to 100 ° C, preferably 55 to 90 ° C, more preferably 65 to 80 ° C. When stored in a high-temperature and high-humidity environment, the resin in the convex portion is plasticized by moisture in the atmosphere, which may cause a decrease in the glass transition temperature. During transportation of the toner or toner cartridge, a high-temperature and high-humidity environment of 40 ° C. and 90% is assumed, and the obtained toner particles are deformed when placed under a certain pressure, or the toner particles adhere to each other. In order to prevent the behavior as particles from being impossible, 45 ° C. or higher is preferable. When used for one-component development, 45 ° C. or higher is preferable in order to prevent the durability against friction from decreasing. Setting the temperature to 100 ° C. or lower is preferable because deterioration of fixability can be prevented.

(External additive)
As the external additive, known inorganic fine particles and polymer fine particles can be preferably used. The primary particle diameter of the external additive is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the external additive used is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass.

  Specific examples of the inorganic fine particles include silica, alumina titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.

  Examples of the polymer fine particles include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as methacrylic acid ester and acrylic acid ester copolymer, silicone, benzoguanamine, and nylon (registered trademark), The polymer particle by a thermosetting resin is mentioned.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

(Toner production method)
The method for producing the toner is not particularly limited, and examples thereof include known wet granulation methods such as a dissolution suspension method, a suspension polymerization method, and an emulsion aggregation method, and a pulverization method. The dissolution suspension method and the emulsion aggregation method (emulsion polymerization method) are preferred from the viewpoint of easy particle size control and shape control.
When obtaining the toner main part as a core by the emulsification method or suspension polymerization method, the convex resin fine particles are added to the system in the process after the toner main part as the core is obtained by the respective known methods. The convex resin fine particles are adhered and fused to the surface of the toner main part. Heating may be performed to promote adhesion and fusion. In addition, the addition of a metal salt is also effective in promoting adhesion and fusion.

(Oil phase creation process)
As a method for preparing an oil phase in which a binder resin, a colorant, etc. are dissolved or dispersed in an organic solvent, the binder resin, the colorant, etc. are gradually added to the organic solvent while stirring and dissolved. Alternatively, it may be dispersed. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable.

As described above, the master batch of the colorant is one of the means, and the same method can be applied to the release agent and the charge control agent.
As another means, it is also possible to obtain a wet master by adding a dispersion aid as required in an organic solvent and dispersing the colorant, the release agent, and the charge control agent in a wet manner.
Further, as another means, if a thing that melts below the boiling point of the organic solvent is dispersed, in the organic solvent, if necessary, a dispersion aid is added and heated with stirring with the dispersoid, Once dissolved, the mixture may be cooled with stirring or shearing to crystallize to produce dispersoid microcrystals.
The colorant, release agent, and charge control agent dispersed using the above means may be further dispersed after being dissolved or dispersed together with the resin in an organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

<Organic solvent>
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. When the resin to be dissolved or dispersed in an organic solvent is a resin having a polyester skeleton, it is better to use an ester solvent such as methyl acetate, ethyl acetate or butyl acetate or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone. Of these, methyl acetate, ethyl acetate, and methyl ethyl ketone are particularly preferred because of their high solvent removal properties.

(Toner main part production process)
There is no particular limitation on the method for preparing a dispersion liquid in which the oil phase obtained in the above-described step is dispersed in an aqueous medium having at least a surfactant to disperse the toner main part composed of the oil phase. Known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. If the dispersion is performed for more than 5 minutes, particles having an undesirably small diameter may remain, or the dispersion may be overdispersed, resulting in instability of the system and generation of aggregates and coarse particles. It is not preferable. The temperature during dispersion is usually 0 to 40 ° C, preferably 10 to 30 ° C. If it exceeds 40 ° C., the molecular motion becomes active, so that the dispersion stability is lowered and aggregates and coarse particles are easily generated, which is not preferable. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases, and the shear energy required for dispersion increases, so that the production efficiency decreases. As the surfactant, the same surfactants as those described in the description of the method for producing the convex resin fine particles can be used. Those are preferred. The surfactant may have a concentration in an aqueous medium of 1 to 10% by mass, preferably 2 to 8% by mass, more preferably 3 to 7% by mass. If it exceeds 10% by mass, the oil droplets will be too small, or a reverse micelle structure will be formed, and the dispersion stability will be lowered, resulting in the coarsening of the oil droplets. On the other hand, if it is less than 1% by mass, the oil droplets cannot be stably dispersed and the oil droplets become coarse, which is not preferable.

<Aqueous medium>
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

<Surfactant>
A surfactant is used to form droplets by dispersing the oil phase in an aqueous medium.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

<Inorganic dispersant>
The dissolved or dispersed toner composition may be dispersed in the aqueous medium in the presence of an inorganic dispersant or resin fine particles. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

<Protective colloid>
The dispersed droplets may be stabilized by a polymer protective colloid.
For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, eg acetic acid Vinyl, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

(Method for forming convex resin)
In the present invention, the convex portion is a raised portion of the surface of the toner base, and its tip tends to have a shape close to a sphere due to surface tension. The method of fusing the convex portions is not limited, and examples thereof include a shape in which a part of the sphere is buried and a shape in which the convex portion is fused in a hemispherical shape.
As a method for forming the convex portion, there is a method in which convex resin fine particles made of at least a resin are separately adhered and fused to a toner main portion that becomes a nucleus having at least a binder resin and a colorant. In order to efficiently attach and fuse the toner main part serving as the core and the convex resin fine particles, it is preferable to disperse these particles in an aqueous medium and control the dispersion stabilizer.
Here, the shape and uniformity of the convex portions are determined by the presence ratio of the surfactant in the aqueous medium, the composition of the convex resin fine particles, and the timing of the fusion process.

  When the dissolution suspension method is used, the above method may be used, but in the state where the oil phase in which the constituent material of the toner main part serving as a nucleus is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium, the convex resin fine particles The toner main part (hereinafter also referred to as core particle) and the convex resin fine particles that adhere to and fuse the convex resin fine particles to the surface of the oil phase droplets can be firmly adhered and fused. Therefore, it is preferable. It is not preferable to add convex resin fine particles during the toner core particle preparation process because the convex portions become coarse and non-uniform.

  The obtained toner main part dispersion liquid can keep the droplets of the core particles stably while stirring. In this state, the convex resin fine particle dispersion is charged and adhered onto the toner main part. The vinyl-based convex resin fine particle dispersion is preferably charged over 30 seconds. If the charging is performed in less than 30 seconds, it is not preferable because the dispersed system is rapidly changed and aggregated particles are generated or the adhesion of vinyl-based convex resin fine particles becomes uneven. On the other hand, it is not preferable from the viewpoint of production efficiency to add to the dark cloud for a long time, for example, exceeding 60 minutes.

The vinyl-based convex resin fine particle dispersion may be diluted or concentrated as appropriate for adjusting the concentration before being added to the core particle dispersion. The concentration of the vinyl-based convex resin fine particle dispersion is preferably 5 to 30% by mass, and more preferably 8 to 20% by mass. If it is less than 5% by mass, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and adhesion of the convex resin fine particles becomes insufficient. Further, if it exceeds 30% by mass, the convex resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the adhesion of the convex resin fine particles becomes non-uniform.
Further, the mass of the surfactant in producing the oil phase droplets is 7% or less, preferably 6% or less, more preferably 5% or less with respect to the mass of the entire aqueous phase. If the mass of the surfactant is 7% or more with respect to the mass of the entire aqueous phase, it is not preferable because the uniformity of the long side length of the convex portion is significantly lowered.

  The vinyl-based convex resin fine particles adhere to the core particles with sufficient strength by the method of the present invention because the core particles freely deform when the vinyl-based convex resin fine particles adhere to the core particle droplets. In order to achieve this, the interface between the vinyl-based convex resin fine particles and the contact surface are sufficiently formed, and the vinyl-based convex resin fine particles are swollen or dissolved by the organic solvent. It seems that the situation will be easy to adhere. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the core particle dispersion, it is 50% by mass to 150% by mass, preferably 70% by mass with respect to the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). It may be in the range of% to 125% by mass. If it exceeds 150% by mass, toner particles obtained in a single production process are reduced and production efficiency is low, and if there is a large amount of organic solvent, dispersion stability is lowered and stable production becomes difficult.

  The temperature at which the vinyl-based convex resin fine particles adhere to the core particles is 10 to 60 ° C, preferably 20 to 45 ° C. If the temperature exceeds 60 ° C, the energy required for production increases and the production environmental load increases. In addition, low acid value vinyl-based convex resin fine particles may be present on the droplet surface, resulting in unstable dispersion. And coarse particles may be generated. On the other hand, when the temperature is less than 10 ° C., the viscosity of the dispersion increases, and adhesion of the convex resin fine particles becomes insufficient, which is not preferable.

The ratio of the resin constituting the convex resin fine particles to the total mass of the toner is 1% to 20%, preferably 3% to 15%, more preferably 5% to 10%. When the content is 1% or more, the effect is sufficiently exhibited, and when the content is 20% or less, it is possible to prevent excessive convex resin fine particles from weakly adhering to the toner core particles and causing filming or the like. .
In addition, there is a method in which the toner particle matrix and the convex resin fine particles are mixed and agitated to mechanically adhere and coat.

<Desolvation process>
In order to remove the organic solvent from the obtained toner particle dispersion, it is possible to employ a method in which the temperature of the entire system is gradually raised while stirring to completely evaporate and remove the organic solvent in the droplets.
Alternatively, the obtained toner particle dispersion can be sprayed into a dry atmosphere with stirring to completely remove the organic solvent in the droplets. Alternatively, the organic solvent may be removed by evaporation under reduced pressure while stirring the toner particle dispersion. The latter two means can be used in combination with the first means.
As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

<Aging process>
When a modified resin having an isocyanate group at the terminal is added, an aging step may be performed in order to advance the elongation / crosslinking reaction of the isocyanate. The aging time is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is usually 0 to 65 ° C, preferably 35 to 50 ° C.

<Washing process>
The toner particle dispersion obtained by the above method contains toner and other auxiliary materials such as a dispersant such as a surfactant. Therefore, washing is performed to remove only the toner particles. . The toner particle cleaning method includes a centrifugal separation method, a vacuum filtration method, a filter press method, and the like, but is not particularly limited in the present invention. Either method can give a cake of toner particles, but if sufficient washing is not possible with a single operation, the obtained cake is again dispersed in an aqueous solvent to form a slurry and toner particles can be obtained by any of the methods described above. You may repeat the process of taking out. Further, if washing is performed by a vacuum filtration method or a filter press method, a method may be employed in which an aqueous solvent is passed through the cake to wash away the secondary material that the toner particles have embraced. As the aqueous solvent used for this washing, water or a mixed solvent obtained by mixing water and alcohol such as methanol or ethanol is used, but water is preferably used in view of cost and environmental load due to wastewater treatment.

<Drying process>
Since the washed toner particles are embracing a large amount of the aqueous medium, only the toner particles can be obtained by drying and removing the aqueous medium. Drying methods such as spray dryers, vacuum freeze dryers, vacuum dryers, stationary shelf dryers, mobile shelf dryers, fluidized tank dryers, rotary dryers, and agitation dryers are used as drying methods. be able to. The dried toner particles are preferably dried until the water content finally becomes less than 1%. If the toner particles after drying are softly agglomerated and inconvenience occurs during use, they can be crushed using equipment such as a jet mill, Henschel mixer, super mixer, coffee mill, auster blender, and food processor. To loosen soft agglomeration.

(Toner particle size)
In order to achieve uniform and sufficient charging in the toner of the present invention, the volume average particle diameter of the toner is preferably in the range of 3 to 9 μm, preferably 4 to 8 μm, more preferably 4 to 7 μm. If it is less than 3 μm, the toner adhesion is relatively increased and the toner operability due to the electric field is lowered, which is not preferable. On the other hand, if it exceeds 9 μm, the image quality such as reproducibility of thin lines is deteriorated.

  The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.25 or less, more preferably 1.20 or less, and further preferably 1.17 or less. preferable. If it exceeds 1.25, the uniformity of the particle size of the toner is low, and the size of the convex portion tends to vary. In addition, since the toner having a large particle size or a small toner in some cases is consumed over time, and the average particle size of the toner remaining in the developing device changes, the optimum developing conditions for developing the remaining toner are deviated. As a result, various phenomena such as charging failure, extreme increase or decrease in the transport amount, toner clogging, and toner spillage are likely to occur.

Examples of the measuring device for the particle size distribution of the toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (D1) of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(About toner shape)
The average circularity of the toner is 0.930 or more, preferably 0.950 or more, more preferably 0.970 or more. If the average circularity is less than 0.930, the flowability of the toner is low, so that problems in development are likely to occur, and the transfer efficiency also decreases.
The average circularity of the toner is measured by a flow type particle image analyzer FPIA-2000. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been previously removed, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the toner are measured by the above apparatus with a dispersion concentration of 3,000 to 10,000 / μl. can get.

  In the case of a toner manufactured by a wet granulation method, the ionic toner constituent material is unevenly distributed in the vicinity of the surface, so that the toner surface layer has a relatively low resistance. As a result, the charging speed of the toner is increased and the charge rising property is improved. However, there is a problem in that the charge retention is poor, that is, the toner charge amount is easily attenuated. In order to improve this, for example, a method of supporting a surface modifying material on the toner surface can be mentioned.

(Regarding the proportion of charge control agent (CCA) present on the surface layer of the toner main part)
The proportion of the charge control agent in the main part is determined by measuring the sample by EDS analysis using a scanning electron microscope (HITACHI S-4800 Scanning Electron Microscope) or energy dispersive X-ray analyzer (EDAX 204B). Mapping was performed for elements composed of elements other than carbon, hydrogen, and oxygen atoms contained in the control agent. Measurement conditions were measured at an acceleration voltage of 20 kV, and mapping was performed at a magnification of 10,000 times. An ultrathin section toner cross section was prepared with a microtome, and the cross section was observed. Specifically, after embedding the toner base in an epoxy resin, a section is taken out using a cryomicrotome to obtain an ultrathin section measurement sample at about 100 nm. When the outline of a toner cross section overlaps the diagonal of a square with a side of 200 nm, the number of dots mapped such as bromine in the square and a square with a side of 3 μm on the toner center (center of gravity in the cross section) The number of mapped dots such as bromine in the medium was counted, and the ratio per unit area was calculated to evaluate how much the charge control agent was concentrated on the surface layer.
As a confirmation that it exists on the surface of the main part, it is possible to map to elements composed of other than carbon, hydrogen, and oxygen atoms contained in the charge control agent. It doesn't matter.

(Measurement of particle size of vinyl-based convex resin fine particles)
The particle diameter of the convex resin fine particles was measured using UPA-150EX (manufactured by Nikkiso Co., Ltd.).
The particle diameter of the convex resin fine particles is 50 to 200 nm, preferably 80 to 160 nm, more preferably 100 to 140 nm. If the thickness is less than 50 nm, it is difficult to form a sufficiently large convex portion on the toner surface, and if it exceeds 200 nm, the convex portion tends to be non-uniform. The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) is preferably 1.25 or less, more preferably 1.20 or less, and even more preferably 1.17 or less. If it exceeds 1.25, the uniformity of the particle diameter of the convex resin fine particles is low, and therefore the size of the convex portion tends to vary.

(Molecular weight measurement (GPC))
The molecular weight of the resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
-Column: KF801-807 (manufactured by Shodex)-Temperature: 40 ° C
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
The number average molecular weight and weight average molecular weight of the resin were calculated from the molecular weight distribution of the resin measured under the above conditions, using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

(Glass transition temperature (Tg) measurement (DSC))
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Solid concentration measurement)
Measurement of the solid content concentration of the oil phase was performed as follows.
On an aluminum pan (about 1 to 3 g) whose mass has been accurately weighed in advance, about 2 g of the oil phase is placed within 30 seconds, and the mass of the placed oil phase is accurately weighed. This is placed in an oven at 150 ° C. for 1 hour to evaporate the solvent, and then taken out of the oven and allowed to cool. Calculate the mass of the oil phase solid by subtracting the mass of the aluminum pan from the total mass of the aluminum pan and the oil phase solid content, and calculate the solid content concentration of the oil phase by dividing by the mass of the oil phase on which it is placed. . The ratio of the amount of the solvent to the solid content in the oil phase is a value obtained by dividing a value obtained by subtracting the mass of the oil phase solid content from the mass of the oil phase (mass of the solvent) by the mass of the oil phase solid content.

(Acid value measurement)
The acid value of the resin is measured according to JIS K1557-1970. A specific measurement method is shown below.
About 2 g of the pulverized sample is precisely weighed (W (g)).
A sample is put into a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved for 5 hours, and then a phenolphthalein solution is added as an indicator.
The solution is titrated with a burette using a 0.1 N potassium hydroxide alcohol solution. The amount of the KOH solution at this time is S (ml). A blank test is performed, and the amount of the KOH solution at this time is defined as B (ml).
The acid value is calculated by the following formula.
Acid value = [(SB) × f × 5.61] / W
(F: Factor of KOH solution)

(About the long side and coverage of convex resin)
The toner is observed with a scanning electron microscope (SEM), and the length of the long side of the convex portion and the coverage of the convex portion with respect to the toner are obtained from the obtained SEM image.
Hereinafter, a method for calculating the long side of the convex portion, the standard deviation, and the coverage will be described with reference to FIG.

<Coverage>
The minimum length of two parallel lines in contact with the toner is obtained, and the respective contact points are designated as A and B.
The coverage of the convex portion with respect to the toner is calculated from the area of a circle whose diameter is the length of the line segment AO with the middle point O of the line segment AB as the center and the area of the convex portion included in the circle.
The coverage is calculated by the above method for 100 or more toner particles, and the average value is obtained.

<Average length of long side>
-It calculates | requires by measuring the length of the long side of 100 or more convex parts about 100 or more toner particles.
-With the length of the long side, two parallel line segments sandwiching the convex portion are drawn as shown in FIG. The distance between the line segments between the positions where each line segment first contacts the convex contour is defined as the side of the convex portion. Of the convex portions and sides, the side having the longest side is defined as the long side of the convex portion.
-Image analysis type particle size distribution measurement software “Mac-View” (manufactured by Mountec Co., Ltd.) was used to measure the area of the convex part and the long side of the convex part.

<Standard deviation>
Long side lengths x ₁ , x ₂ ,. . . , The arithmetic mean m of the population consisting of
It is defined as At this time, using the population mean, the amount obtained as follows:
Is defined as population variance. The positive square root σ of this population variance is defined as the standard deviation.

The average length of the long sides of the protrusions is 0.1 μm or more and less than 0.5 μm, preferably 0.3 μm or less. When the thickness is 0.5 μm or more, the convex portions on the surface become sparse, and the effect of surface modification cannot be obtained. The standard deviation of the average length is 0.2 or less, preferably 0.1 or less. When the standard deviation exceeds 0.2, a problem due to surface non-uniformity occurs.
The coverage is 10% to 90%, preferably 40% to 80%, more preferably 50% to 70%. When the coverage is less than 10%, the background dirt and the heat-resistant storage property are insufficient. On the other hand, if it exceeds 90%, the low-temperature fixability deteriorates.

<Charge control agent particle size>
The particle size of the charge control agent in the convex part is determined by measuring the toner by EDS analysis using a scanning electron microscope (HITACHI S-4800 Scanning Electron Microscope) and energy dispersive X-ray analyzer (EDAX 204B). Metal mapping was performed and evaluated.
Measurement conditions were measured at an acceleration voltage of 20 kV, and mapping was performed at a magnification of 10,000 times. In the continuous portion of the mapping dots, half of the farthest distance between the two points was taken as the particle size of the sample. Assuming that the convex part is a perfect circle, play the diameter line, measure the particle size of all of the sample mapping dots on the diameter line, and calculate the average value of the particle size of the charge control agent in the convex part. It was.

  The charge amount of the toner for developing a dry electrostatic image according to the present invention is such that 45 to 55 g of the toner and 70 to 90 g of alumina beads (φ = 10 mm) are placed in a polyethylene cylindrical container, and the container is charged at a speed of 140 to 160 rpm. It can be set to 95% to 120% of the charge amount of the deteriorated toner prepared by rotating and agitating in a roll mill for 44 hours, and the chargeability is hardly lowered.

<Image forming apparatus and image forming method>
The image forming apparatus of the present invention includes a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier that is exposed based on image data. Exposure means for writing the electrostatic latent image, toner for making the latent image visible, developing means for supplying the toner to the electrostatic latent image formed on the surface of the latent image carrier and developing, and latent image carrier The image forming apparatus includes at least a transfer unit that transfers a visible image on the surface of a body to a transfer target, and a fixing unit that fixes the visible image on the transfer target, and other units that are appropriately selected as necessary. For example, it comprises a static elimination means, a cleaning means, a recycling means, a control means and the like.

  The image forming method of the present invention includes a charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data, and writing an electrostatic latent image, A development process for developing and visualizing the electrostatic latent image formed on the surface of the latent image carrier, a transfer process for transferring the visible image on the surface of the latent image carrier to the transfer body, A fixing step for fixing the visible image, and including at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, For example, a static elimination process, a cleaning process, a recycling process, a control process, etc. are included.

  The electrostatic latent image can be formed by, for example, uniformly charging the surface of the latent image carrier with a charging unit and then exposing the surface of the latent image carrier imagewise with an exposure unit. In the formation of a visible image by the development, a toner layer is formed on a developing roller as a developer carrying member, and the toner layer on the developing roller is conveyed so as to be in contact with a photosensitive drum as a latent image carrying member. Thus, the electrostatic latent image on the photosensitive drum is developed. The toner is stirred by the stirring means and mechanically supplied to the developer supply member. The toner supplied from the developer supply member and deposited on the developer carrier is formed into a uniform thin layer by passing through a developer layer regulating member provided so as to contact the surface of the developer carrier. Further, it is charged. The electrostatic latent image formed on the latent image carrier is developed by attaching the toner charged by the developing means in the developing region to become a toner image. The transfer of the visible image can be performed, for example, by charging the latent image carrier (photoconductor) using a transfer charger, and can be performed by the transfer unit. The transferred visible image is fixed by using a fixing device to transfer the visible image transferred to the recording medium, and may be performed each time the toner of each color is transferred to the recording medium. On the other hand, it may be performed simultaneously at the same time in a state of being laminated. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.

Next, the basic configuration of the image forming apparatus (printer) according to the embodiment of the present invention will be further described with reference to the drawings.
FIG. 3 is a schematic diagram showing the configuration of the image forming apparatus according to the embodiment of the present invention. Here, an embodiment applied to an electrophotographic image forming apparatus will be described. The image forming apparatus includes yellow (hereinafter referred to as “Y”), cyan (hereinafter referred to as “C”), magenta (hereinafter referred to as “M”), black (hereinafter referred to as “K”). The color image is formed from the four color toners.

  First, a basic configuration of an image forming apparatus (tandem type image forming apparatus) that includes a plurality of latent image carriers and parallels the plurality of latent image carriers in the moving direction of the surface moving member will be described. This image forming apparatus includes four photosensitive members (1Y), (1C), (1M), and (1K) as latent image carriers. Although a drum-shaped photoconductor is taken as an example here, a belt-shaped photoconductor can also be adopted. Each of the photoconductors (1Y), (1C), (1M), and (1K) is rotationally driven in the direction of the arrow in the drawing while being in contact with the intermediate transfer belt (10) that is a surface moving member. Each of the photoreceptors (1Y), (1C), (1M), and (1K) is obtained by forming a photosensitive layer on a relatively thin cylindrical conductive substrate and further forming a protective layer on the photosensitive layer. In addition, an intermediate layer may be provided between the photosensitive layer and the protective layer.

  FIG. 4 is a schematic diagram showing the configuration of the image forming unit (2) in which the photoconductor is disposed. Note that the configurations around the photoconductors (1Y), (1C), (1M), and (1K) in the image forming portions (2Y), (2C), (2M), and (2K) are all the same. Only one image forming unit (2) is illustrated, and the codes (Y), (C), (M), and (K) for color classification are omitted. Around the photosensitive member (1), along the surface moving direction, a charging device (3) as a charging unit, a developing device (5) as a developing unit, and a toner image on the photosensitive member (1) are recorded. Alternatively, a transfer device (6) as a transfer means for transferring to the intermediate transfer belt (10) and a cleaning device (7) for removing untransferred toner on the photoreceptor (1) are arranged in this order.

  Between the charging device (3) and the developing device (5), an exposure device (4) serving as an exposure unit that performs exposure based on image data on the surface of the charged photoreceptor (1) and writes an electrostatic latent image. Space is secured so that the light emitted from can pass to the photoconductor (1). The charging device (3) charges the surface of the photoreceptor (1) to a negative polarity. The charging device (3) in this embodiment includes a charging roller as a charging member that performs a charging process by a so-called contact / proximity charging method. That is, the charging device (3) charges the surface of the photosensitive member (1) by bringing the charging roller into contact with or close to the surface of the photosensitive member (1) and applying a negative bias to the charging roller.

  A DC charging bias is applied to the charging roller such that the surface potential of the photoreceptor (1) is -500V. Note that a charging bias in which an AC bias is superimposed on a DC bias can also be used. The charging device (3) may be provided with a cleaning brush for cleaning the surface of the charging roller. As the charging device (3), a thin film may be wound around both end portions in the axial direction on the peripheral surface of the charging roller, and this may be installed so as to contact the surface of the photoreceptor (1). In this configuration, the surface of the charging roller and the surface of the photoreceptor (1) are in close proximity to each other with a distance corresponding to the thickness of the film. Accordingly, a discharge is generated between the surface of the charging roller and the surface of the photoreceptor (1) by the charging bias applied to the charging roller, and the surface of the photoreceptor (1) is charged by the discharge.

  An electrostatic latent image corresponding to each color is formed on the surface of the photosensitive member (1) thus charged by exposure by the exposure device (4). The exposure device (4) writes an electrostatic latent image corresponding to each color on the photoreceptor (1) based on image information corresponding to each color. In addition, although the exposure apparatus (4) of this embodiment is a laser system, the other system which consists of an LED array and an imaging means can also be employ | adopted.

  The toner replenished from the toner bottles (31Y), (31C), (31M), (31K) into the developing device (5) is conveyed by the developer supply roller (5b) and carried on the developing roller (5a). Will be. The developing roller (5a) is conveyed to a region facing the photoreceptor (1) (hereinafter referred to as “developing region”). The developing roller (5a) moves in the same direction in the developing area at a linear velocity faster than the surface of the photoreceptor (1). Then, the toner on the developing roller (5a) supplies the toner to the surface of the photoconductor (1) while rubbing the surface of the photoconductor (1). At this time, a developing bias of −300 V is applied to the developing roller (5a) from a power source (not shown), whereby a developing electric field is formed in the developing region. Then, between the electrostatic latent image on the photoreceptor (1) and the developing roller (5a), an electrostatic force directed toward the electrostatic latent image acts on the toner on the developing roller (5a). As a result, the toner on the developing roller (5a) adheres to the electrostatic latent image on the photoreceptor (1). By this adhesion, the electrostatic latent image on the photoconductor (1) is developed into a corresponding color toner image.

  The intermediate transfer belt (10) in the transfer device (6) is stretched around three support rollers (11), (12) and (13), and is configured to endlessly move in the direction of the arrow in the figure. . On the intermediate transfer belt (10), the toner images on the photoreceptors (1Y), (1C), (1M), and (1K) are transferred so as to overlap each other by the electrostatic transfer method. Although there is a configuration using a transfer charger in the electrostatic transfer system, a configuration using a primary transfer roller (14) in which generation of transfer dust is small is adopted here.

  Specifically, a primary transfer roller (6) as a transfer device (6) is provided on the back surface of the portion of the intermediate transfer belt (10) in contact with each photoconductor (1Y), (1C), (1M), (1K). 14Y), (14C), (14M), and (14K). Here, the portions of the intermediate transfer belt (10) pressed by the primary transfer rollers (14Y), (14C), (14M), and (14K) and the photoreceptors (1Y), (1C), (1M), (1K) forms a primary transfer nip portion.

When the toner images on the photoconductors (1Y), (1C), (1M), and (1K) are transferred onto the intermediate transfer belt (10), positive polarity is applied to each primary transfer roller (14). A bias is applied. As a result, a transfer electric field is formed in each primary transfer nip portion, and the toner images on the photoreceptors (1Y), (1C), (1M), and (1K) are electrostatically transferred onto the intermediate transfer belt (10). Attached and transferred.
Around the intermediate transfer belt (10), there is provided a belt cleaning device (15) for removing toner remaining on the surface thereof. This belt cleaning device (15) is configured to collect unnecessary toner adhering to the surface of the intermediate transfer belt (10) with a fur brush and a cleaning blade. The collected unnecessary toner is transported from the belt cleaning device (15) to a waste toner tank (not shown) by a transport means (not shown). The secondary transfer roller (16) is disposed in contact with the intermediate transfer belt (10) stretched around the support roller (13).

  A secondary transfer nip portion is formed between the intermediate transfer belt (10) and the secondary transfer roller (16), and transfer paper as a recording member is fed into this portion at a predetermined timing. Yes. This transfer paper is housed in a paper feed cassette (20) on the lower side of the exposure device (4) in the drawing, and is fed by a secondary transfer nip by a paper feed roller (21), a pair of registration rollers (22), and the like. It is conveyed to the part. Then, the toner images superimposed on the intermediate transfer belt (10) are collectively transferred onto the transfer paper at the secondary transfer nip portion. During this secondary transfer, a positive bias is applied to the secondary transfer roller (16), and the toner image on the intermediate transfer belt (10) is transferred onto the transfer paper by the transfer electric field formed thereby. A heat fixing device (23) as a fixing unit is disposed downstream of the secondary transfer nip portion in the transfer sheet conveyance direction. The heat fixing device (23) includes a heating roller (23a) with a built-in heater and a pressure roller (23b) for applying pressure. The transfer paper that has passed through the secondary transfer nip is sandwiched between these rollers and receives heat and pressure. As a result, the toner on the transfer paper is melted and the toner image is fixed on the transfer paper. Then, the fixed transfer paper is discharged onto a paper discharge tray on the upper surface of the apparatus by a paper discharge roller (24).

In the developing device (5), the developing roller (5a) as a developer carrying member is partially exposed from the opening of the casing. Further, here, a one-component developer containing no carrier is used. The developing device (5) receives toner of the corresponding color from the toner bottles (31Y), (31C), (31M), and (31K) shown in FIG. The toner bottles (31Y), (31C), (31M), and (31K) are configured to be detachable from the image forming apparatus main body so that they can be replaced individually.
With such a configuration, it is only necessary to replace the toner bottles (31Y), (31C), (31M), and (31K) when the toner ends. Therefore, other components that have not yet reached the end of their life when the toner ends can be used as they are, and the user's expense can be reduced.

  FIG. 5 is a schematic diagram showing the configuration of the developing device (5) in FIG. The developer (toner) in the developer container is agitated by a developer supply roller (5b) as a developer supply member, and carries the developer supplied to the photoreceptor (1) on the surface thereof. It is carried to the nip portion of the developing roller (5a) as a body. At this time, the developer supply roller (5b) and the developing roller (5a) are rotated in the reverse direction (counter rotation) at the nip portion. Further, the amount of toner on the developing roller (5a) is regulated by a regulating blade (5c) as a developer layer regulating member provided so as to be in contact with the developing roller (5a), and a toner thin film is formed on the developing roller (5a). A layer is formed. Further, the toner is rubbed between the developer supply roller (5b), the nip portion of the developing roller (5a), the regulating blade (5c), and the developing roller (5a), and is controlled to an appropriate charge amount.

  FIG. 6 is a schematic view showing an example of the configuration of the process cartridge. The toner of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG. In the present invention, the process cartridge includes a latent image carrier, and at least a latent image on the latent image carrier among the components such as a latent image carrier, a charging unit, a developing unit, and a latent image carrier. A developing device for developing using toner is integrally coupled, and this process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer. The process cartridge shown in FIG. 6 includes a latent image carrier, a charging unit, and the developing unit described with reference to FIG.

  Examples are shown below, but the scope of the present invention is not limited by these Examples. Moreover, the part in an Example shows a mass part.

[Production of Br-CA]
250 parts of 4-bromobiphenyl-4′-ol, 30 parts of formaldehyde and 1 part of sodium hydroxide were added to 200 parts of diphenyl ether, and the mixture was heated to reflux at reflux temperature for 1 hour. After refluxing, the solvent was removed, filtered, and washed sufficiently to obtain a halogenated calixarene [Br-CA] represented by the following formula as white crystals. N in the formula is 4 to 24.

[Manufacture of dispersion 1 for convex resin]
In 498 parts of ion-exchanged water, 0.7 part of sodium dodecyl sulfate was added and dissolved by heating to 80 ° C. to obtain an aqueous medium. Separately, 170 parts of styrene and 30 parts of butyl acrylate were added and stirred to obtain a uniform monomer solution. The obtained monomer solution was put into an aqueous medium, and ultrasonic monomer was applied at 90 to 110 W for 10 minutes using an ultrasonic homogenizer VCX750 (SONICS & MATERIALS Inc.) to disperse the monomer solution in the aqueous medium. In the middle, the liquid temperature increased by ultrasonic irradiation, but the water temperature was adjusted so as not to exceed 50 ° C. with a water bath or the like. The obtained dispersion was transferred into a reaction vessel equipped with a stirrer and a nitrogen introduction tube during cooling, and maintained at 60 ° C. with stirring, and 2.6 parts of potassium persulfate was dissolved in 104 parts of ion-exchanged water. The polymerization reaction was carried out for 120 minutes. Thereafter, the mixture was cooled to obtain white [convex resin dispersion 1] having a volume average particle diameter of 126 nm. The obtained [resin dispersion for convex part 1] was placed in a 2 ml petri dish, and the dried product obtained by evaporating the dispersion medium was measured. The weight average molecular weight was 95,000 and Tg was 52 ° C.

[Production of convex resin dispersion 2]
Except for adding 20 parts of BONTRON E-108 (trademark; Orient Chemical Industry Co., Ltd.) (charge control agent) in the step of obtaining a uniform monomer solution, the same as [Dispersion for convex resin 1] [Dispersion liquid 2 for convex resin] was obtained.

[Production of convex resin dispersion 3]
Except that 20 parts of BONTRON E-84 (trademark; Orient Chemical Industry Co., Ltd.) (charge control agent) was further added in the step of obtaining a uniform monomer solution, the same as [Dispersion liquid 1 for convex resin] [Dispersion liquid 3 for convex resin] was obtained.

[Production of convex resin dispersion 4]
[Protrusion resin dispersion 4] was obtained in the same manner as [Protrusion resin dispersion 1] except that 20 parts of [Br-CA] was further added in the step of obtaining a uniform monomer solution.

<Synthesis of polyester 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 264 parts of bisphenol A ethylene oxide 2-mole adduct, 523 parts of bisphenol A propylene oxide 2-mole adduct, 123 parts terephthalic acid, 173 parts adipic acid and dibutyl 1 part of tin oxide was added and reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 8 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 26 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 4000, a weight average molecular weight of 47000, Tg of 65 ° C., and an acid value of 12.

-Synthesis of isocyanate-modified polyester 1-
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. under normal pressure for 8 hours. Next, it was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize [Intermediate Polyester 1]. The obtained [Intermediate polyester 1] has a number average molecular weight of 2,200, a weight average molecular weight of 9,700, a glass transition temperature of 54 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 52 mgKOH / g. there were.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Modified polyester 1] was obtained.

-Creating a master batch-
Carbon black (Cabot Legal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 acid value 10, Mw 20,000, Tg 64 ° C.): 60 parts, water: 30 parts are mixed in a Henschel mixer. Thus, a mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mm with a pulverizer to obtain [Masterbatch 1].

[Example 1]
Toner manufacturing process <oil phase preparation process>
In a container equipped with a stir bar and a thermometer, 545 parts of [Polyester 1], 181 parts of [paraffin wax (melting point 74 ° C.)] and 1450 parts of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring and remains at 80 ° C. After holding for 5 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 655 parts of a 66% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1].
[Pigment / WAX Dispersion 1] 976 parts were mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, and then [Isocyanate-modified polyester 1] 88 parts, BONTRON E-108 (Orient Chemical Co., Ltd.) (Company) (charge control agent) was added in 5 parts and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute to obtain [Oil Phase 1]. It was 52.0 mass% when solid content of the obtained [oil phase 1] was measured, and the quantity of ethyl acetate with respect to solid content was 92 mass%.

<Water phase creation process>
970 parts of ion-exchange water, 40 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether When 95 parts of a 48.5% aqueous solution of sodium disulfonate and 98 parts of ethyl acetate were mixed and stirred, the pH reached 6.2. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 9.5 to obtain [Aqueous Phase 1].

<Core particle creation process>
Add 1200 parts of [Aqueous Phase 1] to the obtained [Oil Phase 1], and cool in a water bath to suppress the temperature rise due to shear heat of the mixer so that the temperature in the liquid is in the range of 20-23 ° C. , Adjusted at a speed of 8,000-15,000 rpm using a TK homomixer and mixed for 2 minutes, then adjusted at a speed of 130-350 rpm with a three-one motor with an anchor blade attached for 10 minutes The mixture was stirred to obtain [core particle slurry 1] in which droplets of an oil phase serving as core particles were dispersed in an aqueous phase.

<Formation of convex resin part>
[Core Dispersion Liquid 2] 106 parts in a state where the liquid temperature is 22 ° C. while stirring the [core particle slurry 1] with a three-one motor with an anchor blade attached at a rotational speed of 130 to 350 rpm. And 71 parts of ion-exchanged water (solid content concentration 15%) were added dropwise over 3 minutes. After dropping, the number of rotations was adjusted to 200 to 450 rpm, and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 1]. When 1 ml of [Composite Particle Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was transparent.

<Desolvation process>
[Composite particle slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1]. [Dispersion slurry 1] was placed on a small amount of slide glass, and the state was observed at 200 times magnification with an optical microscope with a cover glass in between. As a result, a uniform toner main part was observed. Further, when 1 ml of [Dispersion Slurry 1] was taken and diluted to 10 ml and centrifuged, the supernatant was transparent.

<Washing and drying process>
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner Base 1]. When the obtained [Toner Base 1] was observed with a scanning electron microscope, the convex portions were uniformly attached to the surface of the core particles. The average length of the long sides of the convex portions of [Toner Base 1] was 0.22 μm, and its standard deviation was 0.11. The coverage was 64%. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 15000. These results are summarized in Table 1.

[Example 2]
The same procedure as in Example 1 was performed except that [Dispersion for convex resin 2] in Example 1 was changed to [Dispersion for convex resin 3]. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 16000.
[Example 3]
The same procedure as in Example 1 was performed except that [Dispersion for convex resin 2] in Example 1 was changed to [Dispersion for convex resin 4]. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 14000.

[Example 4]
The same operation as in Example 1 was conducted except that E-108 in [Pigment / WAX Dispersion 1] in Example 1 was changed to E-84. The presence ratio of the charge control agent was determined with the target being zinc element. The zinc count ratio on the surface was center: surface layer = 1: 1000.
[Example 5]
The same operation as in Example 4 was performed except that [Dispersion for convex resin 2] in Example 4 was changed to [Dispersion for convex resin 3]. The presence ratio of the charge control agent was determined with the target being zinc element. The zinc count ratio on the surface was center: surface layer = 1: 900.
[Example 6]
The same operation as in Example 4 was performed except that [Dispersion for convex resin 2] in Example 4 was changed to [Dispersion for convex resin 4]. The presence ratio of the charge control agent was determined with the target being zinc element. The zinc count ratio on the surface was center: surface layer = 1: 1100.

[Example 7]
The same procedure as in Example 1 was performed except that E-108 in [Pigment / WAX dispersion 1] of Example 1 was changed to [Br-CA]. The bromine count ratio on the surface was center: surface layer = 1: 5200.
[Example 8]
The same procedure as in Example 7 was performed except that [Dispersion liquid 2 for convex resin] in Example 7 was changed to [Dispersion liquid 3 for convex resin]. The bromine count ratio on the surface was center: surface layer = 1: 1100.
[Example 9]
The same operation as in Example 7 was carried out except that [Dispersion for convex resin 2] in Example 7 was changed to [Dispersion for convex resin 4]. The bromine count ratio on the surface was center: surface layer = 1: 4300.

[Example 10]
Example 1 except that 106 parts of [Dispersion for convex resin 2] and 71 parts of ion-exchanged water are changed to 312 parts of [Dispersion for convex resin 2] and 213 parts of ion-exchanged water in Example 1. And so on. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 5000.
[Example 11]
Example 1 except that 106 parts of [Dispersion for convex resin 2] and 71 parts of ion-exchanged water in Example 1 were changed to 12 parts of [Dispersion for convex resin 2] and 9 parts of ion-exchanged water. And so on. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 15000.

[Comparative Example 1]
Example 1 except that E-108 is not added to [Pigment / WAX Dispersion 1] of Example 1 and [Dispersion 2 for Convex Resin 2] is changed to [Dispersion 1 for Convex Resin]. The same was done.
[Comparative Example 2]
The same procedure as in Example 4 was performed except that [Dispersion for convex resin 2] in Example 4 was changed to [Dispersion for convex resin 1].
[Comparative Example 3]
The same operation as in Example 7 was performed except that [Dispersion for convex resin 2] in Example 7 was changed to [Dispersion for convex resin 1]. The bromine count ratio on the surface was center: surface layer = 1: 1200.
[Comparative Example 4]
Comparative Example 1 was performed in the same manner as Comparative Example 1 except that [Dispersion for convex resin 1] was changed to [Dispersion for convex resin 2].
[Comparative Example 5]
In Example 5, it carried out like Example 5 except having performed in the state whose liquid temperature in <formation of a convex part resin part> was 50 degreeC.

[Comparative Example 6]
Example 1 except that 106 parts of [Dispersion for convex resin 2] and 71 parts of ion-exchanged water were changed to 10 parts of [Dispersion for convex resin 2] and 8 parts of ion-exchanged water in Example 1. And so on. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 15000.
[Comparative Example 7]
Example 1 except that 106 parts of [Dispersion for convex resin 2] and 71 parts of ion-exchanged water in Example 1 were changed to 500 parts of [Dispersion for convex resin 2] and 350 parts of ion-exchanged water. And so on. The presence ratio of the charge control agent was determined with the target being an aluminum element. The aluminum count ratio on the surface was center: surface layer = 1: 4000.

-Production of carrier-
To 100 parts of toluene, 100 parts of silicone resin (organostraight silicone), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed for 20 minutes with a homomixer. A layer coating solution was prepared.
Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having a volume average particle size of 50 μm to prepare [Carrier 1].

-Production of developer-
Each developer of Examples 1 to 11 and Comparative Examples 1 to 7 was prepared by mixing 5 parts of each toner and 95 parts of [Carrier 1].

[Evaluation method]
Next, the chargeability was evaluated as follows using each of the obtained developers.
<Chargeability>
Conductive toner carrier capable of carrying toner on its surface, toner supply means provided opposite to the toner carrier, for supplying charged toner to the toner carrier, the toner carrier, and the toner A power source for forming an electric field for adhering the toner to the toner carrier, a driving unit for driving the toner carrier and the toner supply unit, and a charge amount of the toner adhered to the surface of the toner carrier. Charge amount measuring means for measuring the toner, and the charged toner is attached to the toner supply means, and the toner on the toner supply means is transferred to the toner carrier by electrostatic force, and the toner is transferred to the toner carrier. A charge amount of the toner carrier in a state where the toner carrier is attached to the toner carrier; and a charge amount of the toner carrier in a state where the toner is removed from the toner carrier. Measuring the charge amount of the toner from both the charge difference between the two was measured. Specifically, it is a cylindrical developing roll as an example of a toner supply unit, and is made of a conductive material such as aluminum, nonmagnetic stainless steel, copper, or brass. As is well known, a magnet having a plurality of magnetic poles is provided inside the developing roller, and a uniform toner layer is formed on the outer peripheral surface by the magnetic force of the magnet. A developing roll as an example of a toner carrier, which is made of a metal such as aluminum, stainless steel, copper brass, or a conductive material such as conductive plastic. A bias voltage is applied to each of the developing roll and the developing roll, and each bias voltage can be changed separately. These bias voltages are variously set according to whether the toner layer is formed on the developing roll or the toner layer is formed on the developing roll by the reversal developing system according to the charging polarity of the toner and the normal developing system. The By applying a bias voltage and driving and rotating the developing roll and the developing roll, the developing roll is developed by electrophotography, and a uniform toner layer is formed on the developing roll. As a result of the toner layer being formed on the developing roll, the amount of charge held by the developing roll increases as compared with that before development. Therefore, the amount of charge held by the developing roll is measured. Further, the mass of the toner on the developing roll is measured by measuring the mass of the developing roll with the toner carried thereon and the mass after removing the toner with a balance. From the charge amount Q and mass of the obtained toner, that is, the mass M, a measured value Q / M (charge amount per unit mass) of a parameter indicating development characteristics of the toner is obtained.
This time, 5.000 g of developer corresponding to each toner sample was put in a stainless steel container having a bottom diameter of 25 mm and a height of 30 mm, and the rotation of 200 rpm was applied in the circumferential direction for 5 minutes, and the toner and the carrier were stirred and brought into contact with each other. . The agitated toner samples were evaluated by the above measurement method, and the Q / M of each was measured.

Furthermore, by using the surface area calculated from the volume average particle diameter measured by the following Coulter counter method, it can be converted into Q / A (charge amount per unit area). 0.1 to 5 mL of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of the measurement sample is further added as a solid content. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained. The toner density was assumed to be 1.10 gcm ^−3, and the evaluation was performed by converting from Q / M to Q / A using the value of Dv.

  As a method for evaluating a deteriorated sample, 45 to 55 g of toner to be deteriorated and 70 to 90 g of alumina beads (φ = 10 mm) are placed in a polyethylene cylindrical container, such as an eyeboy 250 ml container, and a rotational speed of 140 to 160 rpm. Then, the container was rotated on a roll mill for 44 hours and stirred to produce a deteriorated toner, and the above-mentioned charging property was measured and evaluated.

Judgment criteria regarding the charging property and the charging property at the time of deterioration are as follows.
A: Charge amount (q) satisfies a relational expression of −22 μC / m ² > q ○: Charge amount (q) satisfies a relational expression of −18 μC / m ² > q ≧ −22 μC / m ² Δ: Charge amount (q) satisfies the relational expression of −12 μC / m ² > q ≧ −18 μC / m ² ×: Charge amount (q) satisfies the relational expression of q ≧ −12 μC / m ²

The criteria for determining the chargeability of the deterioration difference are as follows.
A: Charge amount (q) and deteriorated charge amount (q _d ) satisfy the relational expression 5 ≧ {− (q−q _d ) / q} * 100 ≧ −5: Charge amount (q) and deteriorated charge The quantity (q _d ) does not correspond to ◎,
10 ≧ {− (q−q _d ) / q} * 100 ≧ −10 satisfying the relational expression Δ: Charge amount (q) and deteriorated charge amount (q _d ) do not correspond to ○,
15 ≧ {− (q−q _d ) / q} * 100 ≦ 100 ≦ -15 ×: Charge amount (q) and deteriorated charge amount (q _d ) do not correspond to Δ

The total score is as follows: ◎ = 3, ○ = 2, Δ = 1, x = 0, and calculated by multiplying the determination of chargeability, chargeability during deterioration, and deterioration difference. The results are summarized in Table 2.

Next, using each of the obtained toners, background stain, anti-sticking property, fixing property (fixing lower limit temperature, hot offset), accelerated aggregation, and penetration were evaluated as follows.
<Skin dirt>
Using a color electrophotographic device (IPSiO SP C220), after printing 2,000 white solid images, the toner adhered on the photoconductor during printing of the white solid image was peeled off with scotch tape and pasted on white paper, and the spectral density ΔE was measured using a meter and evaluated in four stages.
◎ ・ ・ ・ ΔE is less than 3 ○ ・ ・ ・ ΔE is 3 or more and less than 5 △ ・ ・ ・ ΔE is 5 or more and less than 10 × ・ ・ ・ ΔE is 10 or more

<Fixing resistance>
Using a color electrophotographic apparatus (IPSIO SP C220), after the output of 2,000 white solid images, the toner adhered to the regulating blade was evaluated in four stages.
◎ ・ ・ ・ Toner adhesion is very good level ○ ・ ・ ・ Toner adhesion is not noticeable and does not affect image quality △ ・ ・ ・ Toner adhesion is a level that affects image quality × ・ ・ ・ Toner adhesion is conspicuous , Level that greatly affects image quality

<Fixing temperature limit>
A black solid unfixed image of 1.0 mg / cm ² was formed on plain paper using a fixing unit of a color electrophotographic apparatus (IPSIO SP C220). The temperature at which there was no problem in image quality was set as the minimum fixing temperature, while changing the heating temperature.
◎ ・ ・ ・ less than 140 ℃ ○ ・ ・ ・ 140 ℃ or more and less than 150 ℃ △ ・ ・ ・ 150 ℃ or more and less than 160 degrees × ・ ・ ・ 160 ℃ or more

<Hot offset>
Using a fixing unit of a color electrophotographic apparatus (IPSIO SP C220), a solid black unfixed image of 1.0 mg / cm ² was formed on plain paper and fixed at different fixing temperatures. The temperature at which hot offset occurs was measured and evaluated in four stages.
◎ ・ ・ ・ 190 ℃ or more ○ ・ ・ ・ 180 ℃ or more and less than 190 ℃ △ ・ ・ ・ 170 ℃ or more and less than 180 ℃ × ・ ・ ・ less than 170 ℃

<Accelerated cohesion>
The accelerated aggregation degree of the toner is measured using a Bowder Tester PT-R manufactured by Hosokawa Micron. A sieve having an opening of 20 μm, 45 μm, or 75 μm was used. The acceleration aggregation degree of the toner sample after being left for 24 hours at 25 ° C. and 50% environment and after being left for 24 hours at 40 ° C. and 90% environment was measured, and the difference between the values was evaluated.
◎ ・ ・ ・ The difference is less than 2.5% ○ ・ ・ ・ The difference is 2.5 or more and less than 5.0% △ ・ ・ ・ The difference is 5.0 or more and less than 7.5% × ・ ・ ・ The difference is 7.5 %that's all

<Penetration>
A 10 g sample is placed in a 30 mL screw tube bottle, placed in a thermostatic chamber (DK340S) and allowed to stand at 40 ° C. and 90% for 24 hours, and then the sample is taken out and allowed to cool at room temperature. The penetration was measured with a penetration tester and evaluated in four stages.
◎ ・ ・ ・ 15.0mm or more ○ ・ ・ ・ 10.0mm or more and less than 15.0mm △ ・ ・ ・ 5.0mm or more and less than 10.0mm × ・ ・ ・ less than 5.0mm

These results are summarized in Table 3.

1, 1Y, 1C, 1M, 1K Latent image carrier 2, 2Y, 2C, 2M, 2K Image forming unit 3 Charging device 4 Exposure device 5 Development device 5a Developer roller 5b Developer supply roller 5c Regulating blade 6 Transfer device 7 Cleaning device 10 Intermediate transfer belt 11, 12, 13 Support rollers 14, 14Y, 14C, 14M, 14K Primary transfer roller 15 Belt cleaning device 16 Secondary transfer roller 20 Paper feed cassette 21 Paper feed roller 22 Registration roller pair 23 Heat fixing Device 23a Heating roller 23b Pressure roller 24 Paper discharge roller 31Y, 31C, 31M, 31K Toner bottle

JP 2008-89918 A JP 2011-81258 A

Claims (10)

A toner for dry electrostatic charge image development having a sea-island structure with the main part of the toner as the sea and the convex part as an island,
The main part contains at least a binder resin, a colorant and a charge control agent ,
The charge control agent contained in the main part is unevenly distributed on the surface of the main part;
The convex portion includes at least a resin and a charge control agent,
The average length of the long side of the convex part is 0.1 μm or more and less than 0.5 μm,
The standard deviation of the length of the long side of the convex part is 0.2 or less,
A toner for developing a dry electrostatic charge image, wherein the coverage of the convex portions is 10% to 90%.   The toner for developing a dry electrostatic image according to claim 1, wherein the charge control agent contained in the convex portion has at least a phenolate skeleton.   3. The dry electrostatic charge image developing toner according to claim 1, wherein the charge control agent contained in the main part is calixarene.   4. The dry electrostatic charge image developing toner according to claim 3, wherein the calixarene is a halogenated calixarene.   The dry electrostatic image developing toner has a toner halogen concentration in the square of 3 μm on one side of the center of the toner when the contour of the toner cross section overlaps the diagonal of the square with a side of 200 nm in the cross section. The dry electrostatic image developing toner according to claim 4, wherein the toner has a halogen concentration in a square of 500 to 50,000 times.   The resin contained in the convex part is a vinyl resin, and the vinyl resin is a resin obtained by polymerizing a monomer mixture containing at least a styrene monomer. The toner for developing a dry electrostatic image as described.   The resin contained in the convex portion is a vinyl resin, and the vinyl resin is a resin obtained by polymerizing a monomer mixture containing an acrylate ester. Toner for developing a dry electrostatic image.   The charge amount of the dry electrostatic image developing toner is 45 to 55 g of the toner and 70 to 90 g of alumina beads (φ = 10 mm) are put in a polyethylene cylindrical container, and the container is left at a speed of 140 to 160 rpm for 44 hours. The toner for dry electrostatic charge development according to any one of claims 1 to 7, wherein the toner is 95% to 120% of a charge amount of a deteriorated toner produced by rotating and stirring with a roll mill. A latent image carrier for carrying a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
A toner that visualizes the latent image;
Developing means for supplying and developing toner on the electrostatic latent image formed on the surface of the latent image carrier;
Transfer means for transferring the visible image on the surface of the latent image carrier to the transfer target;
Fixing means for fixing a visible image on the transfer target;
An image forming apparatus comprising:
An image forming apparatus, wherein the toner is a toner for developing a dry electrostatic image according to claim 1. A charging step for uniformly charging the surface of the latent image carrier;
An exposure process for exposing the surface of the charged latent image carrier based on the image data and writing an electrostatic latent image;
A development step of developing the electrostatic latent image formed on the surface of the latent image carrier to visualize it;
A transfer step of transferring a visible image on the surface of the latent image carrier to the transfer target;
A fixing step for fixing a visible image on the transfer target;
Have
An image forming method comprising using the toner for developing a dry electrostatic image according to claim 1 in the developing step.