JP5392459B2 - Toner, developer, image forming method, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., and a developer, a container containing the toner, an image forming method, an image forming apparatus, and a process cartridge using the toner. About.

Images from electrophotographic devices, electrostatic recording devices, and the like are generally not yet satisfactory levels for users familiar with printing. For this reason, there is a demand for higher image quality that satisfies high-definition and high-resolution approaching photography and printing. Development of a toner having a smaller particle size and a narrow particle size distribution is indispensable for improving the image quality of the electrophotographic image.
As the toner, conventionally, pulverized toner is used in an electrophotographic apparatus. This is manufactured by melt-mixing a colorant, a charge control agent, an anti-offset agent and the like in a thermoplastic resin and uniformly dispersing the mixture, and then pulverizing and classifying the obtained solid composition. In such a manufacturing method, a toner having a high range of particle size distribution is easily formed. Therefore, in order to obtain a copy image having good resolution and gradation, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more must be removed by classification. Therefore, the toner obtained by this pulverization method has a low yield. In particular, in the case of a color toner, it is difficult to uniformly disperse a colorant, a charge control agent, and the like in a thermoplastic resin with a toner by a pulverization method. Therefore, even if the compounding agent is dispersed non-uniformly and pulverized, the resulting toner has problems in fluidity, developability, durability, image quality, and the like.

  On the other hand, in recent years, wet granulation by, for example, suspension polymerization, emulsion polymerization (sometimes referred to as polymerization wet granulation), polymer suspension (sometimes referred to as non-polymerization wet granulation), etc. Law toners are known.

Among these wet granulation methods, a suspension polymerization toner is prepared by suspending a toner composition such as a polymerizable monomer, a polymerization initiator and a colorant in an aqueous medium containing a dispersant. Obtained by polymerization. The problem with the toner produced by this method is that the raw materials that can be used are limited to styrene-acrylic resin and the like, and polyesters that are particularly suitable for full-color toners cannot be applied. In addition, it is difficult to control the molecular weight distribution to achieve both low temperature fixability and hot offset resistance (double peaking), and delicate control is difficult, and the shape of the toner particles to be manufactured is spherical. There is a problem that cleaning defects are likely to occur during the formation process.
In addition, a toner by an emulsion polymerization method is obtained by emulsifying a polymerizable monomer and a polymerization initiator in water containing a surfactant and polymerizing the resultant, and agglomerating and fusing the obtained fine particles. This toner is irregularly shaped particles, and is superior to the suspension polymerization toner in the above-described cleaning properties. However, like suspension polymerization toner, polyester is difficult to use. Further, it is difficult to control the molecular weight, and the surfactant is unnecessary after the toner particles are formed. It is difficult to remove the surfactant only on the surface of the toner, and even if the surfactant on the surface can be removed, it remains in the toner particles in a large amount, and the toner charging instability and the charge amount distribution are only broadened. It also causes soiling. Further, if a small amount remains, there is a problem that the photosensitive member, the charging roller, the developing roller and the like are contaminated and the original charging ability is lowered.

  On the other hand, in the polymer suspension method, a polymer as a binder resin and other toner compositions are dispersed and dissolved in a low-boiling organic solvent, and this is emulsified in an aqueous medium containing a dispersant to form droplets. This is a method of removing a low boiling point organic solvent (volatile solvent), and this method is an underwater granulation method without a polymerization reaction. This method is excellent in that polyester can be used, but includes a step of dispersing or dissolving a toner composition containing a binder resin in a solvent. For this reason, there is a problem that high molecular weight resins, cross-linked resins, and the like cannot be used, and the fixing characteristics cannot be satisfactorily controlled.

In addition, wide color reproducibility with toner is required in order to improve the image quality of a full-color image to the same level as printing in electrophotographic image formation. This is achieved for the first time by highly dispersing a colorant excellent in transparency, light resistance and heat resistance in the toner.
However, the polymerization or non-polymerization wet granulation method described above does not include a step of uniformly mixing the toner material by applying a high shearing force, such as the kneading step in the pulverization method. For this reason, it is difficult to achieve uniform and fine colorant dispersion. Further, even if a uniform dispersion state is obtained at the beginning of the granulation step, the dispersion stability of the colorant in the liquid deteriorates and reaggregates in the granulation step. There are problems that the color reproducibility and image density are remarkably deteriorated due to uneven distribution at the interface with water, and the chargeability and stability of the toner are impaired because the pigment is unevenly distributed at the interface.

Thus, in order to improve an electrophotographic image to a print-like image, it is necessary to ensure uniform dispersibility of the pigment in the toner. As such an invention, for example, Patent Document 1 discloses an invention of a toner in which a color material is dispersed by a synergist and a polymer dispersant. This publication discloses that a pigment derivative or the like is added as a synergist in order to enhance the interaction between the pigment and the polymer dispersant. The synergist described in this publication has an ionic functional group in order to develop an interaction with the polymer dispersant. There is a problem that the toner is accelerated and causes a reduction in the coloring power and color reproducibility of the toner.
Patent Document 2 discloses an invention in which a pigment dispersant is added to a master batch to improve the dispersibility of the pigment. However, even if the present invention is applied as it is, it is still unsatisfactory to obtain a good toner by emulsifying or dispersing the toner material in an aqueous system.

Japanese Patent Laid-Open No. 11-231572 JP 2004-126160 A

  The present invention has been made in view of the above-described problems in a toner obtained by a production method including an aqueous granulation step in the aqueous system as described above, and in a toner obtained by a production method including an aqueous granulation step. By using a specific pigment dispersant, the pigment dispersibility is improved, the color reproduction range is expanded, the offset property, the charging property and the storage property are excellent, and the OHP transparency is clearer than the offset printing. And a developer using the toner, a container containing the toner, an image forming method, an image forming apparatus, and a process cartridge.

Means for solving the above problems are as follows. That is,
(1) It contains a toner material containing at least a binder resin, a pigment, and a pigment dispersant. The pigment dispersant contains a polyurea pigment dispersant, and the acid value of the pigment dispersant is 0.01 mgKOH. / G to 1 mgKOH / g and an amine value of 0.01 mgKOH / g to 1 mgKOH / g and granulated by dispersing or emulsifying the solution or dispersion containing the toner material in an aqueous medium. Toner.
(2) The toner according to (1) the melting point of the pigment dispersing agent, which is a 20 ° C. to 80 ° C..
(3) the content of the pigment dispersing agent, the toner according to (1) or (2), characterized in that at most 50 parts by 1 part by mass or more with respect to 100 parts by weight of the pigment.
(4) The toner according to any one of the toner material, characterized in that it further contains a wax (1) to (3).
(5) The toner according to (4) , wherein the wax is paraffin wax.
(6) The toner according to (4) , wherein the wax is a microcrystalline wax.
(7) The toner according to any one of (4) to (6) , wherein the wax has a melting point of 60 ° C to 100 ° C.
(8) The toner according to any one of (4) to (6) , wherein the wax has a melting point of 70 ° C to 90 ° C.
(9) A dispersion containing a binder resin precursor made of a modified polyester resin and an oil phase to which a fine particle dispersant is added are introduced into an aqueous medium, and the compound that extends or crosslinks with the binder resin precursor is dissolved. after the that the oil phase the aqueous medium dispersed in and an emulsified dispersion, wherein the emulsified dispersion liquid of the binder resin precursor in crosslinked or elongation reaction granulation The toner according to any one of (1) to (8) .
(10) The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and the shape factor SF-1 of the toner is 110 to 150. The toner according to any one of (1) to (9) , wherein the toner is present.
(11) A developer containing the toner according to any one of (1) to (10) .
(12) an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and An image forming method comprising at least a transfer step of transferring a visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium,
The toner is the toner according to any one of (1) to (10) .
(13) An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible An image forming apparatus having at least developing means for forming an image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The toner is the toner according to any one of (1) to (10) .
(14) At least an electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forming an image A process cartridge that is detachable from the apparatus body,
The toner is the toner according to any one of (1) to (10) .

  According to the present invention, conventional problems can be solved, and by using a specific pigment dispersant in the toner, the dispersibility is improved, the color reproduction range is widened, the offset property, the chargeability, and the storage Toner that has excellent properties, has OHP transparency, is safe for the environment and the human body, and can achieve clearer image quality than plain offset printing on plain paper, and a developer, toner-containing container, and image using the toner A forming method, an image forming apparatus, and a process cartridge can be provided.

<Pigment dispersant>
When the pigment dispersant used in toner production has an acid value and an amine value, the pigment dispersant generally has an ion-bonding functional group. Conventionally, pigment dispersants are considered to improve the dispersibility of the pigment by adsorbing these ion-binding functional groups on the pigment surface. In a toner obtained by granulation in an aqueous system as in the present invention, since the ion-binding functional group as described above on the pigment dispersant has a high affinity with water, the pigment adsorbed with the pigment dispersant can be used. From the toner to the aqueous phase, or the pigment is unevenly distributed on the toner surface. As a result, the coloring power of the toner may be reduced, and the color reproducibility of the toner may be reduced.
Since the pigment dispersant used in the toner of the present invention has substantially no ionic functional group, the above-mentioned problem does not occur. Further, even in a production method in which a toner material is dissolved and emulsified or dispersed in an aqueous phase, a toner produced using a pigment dispersant having no ionic functional group has improved pigment dispersibility.
That is, the pigment dispersant used in the toner of the present invention has substantially no ionic group. More specifically, the acid value of the pigment dispersant used in the toner of the present invention is 1 mgKOH / g or less, and the amine value of the pigment dispersant is 1 mgKOH / g or less. For example, the acid value of the pigment dispersant used in the toner of the present invention is 0.01 mgKOH / g or more and 1 mgKOH / g or less, and the amine value of the pigment dispersant is 0.01 mgKOH / g or more and 1 mgKOH / g or less. It is preferable that When the acid value and amine value of the pigment dispersant exceeds 1 mgKOH / g, the pigment may be unevenly distributed on the toner surface. When the pigment on the toner surface is unevenly distributed, the interaction between the pigments becomes strong, and the dispersion stability of the pigment is deteriorated. In addition, the toner surface has a higher viscosity than the inside, and it is presumed that an irregularly shaped toner can be obtained due to poor followability on the toner surface during the solvent removal step. As described above, in the present invention, a toner is obtained by using a pigment dispersant that does not substantially have an ion-bonding functional group. Therefore, uneven distribution of the pigment near the surface of the toner is prevented, and the above-described problems are not caused. Toner is obtained.
The pigment dispersant used in the present invention is preferably optimized in content in the toner in order to satisfy the above-described characteristics. When the content of the pigment dispersant in the toner is small, the pigment dispersibility deteriorates, and when the content in the toner is large, the above-described storage stability, charging characteristics, and fixing characteristics may be deteriorated.

  The pigment dispersant used in the present invention has an optimum polymer dispersant according to the binder resin to be used. When a polyester resin is used as the binder resin, the use of the polyester polymer dispersant is Is the best. This is considered to be caused by the chemical interaction between the binder resin and the ester group of the polymer dispersant. A polyurethane polymer dispersant is also preferred. It can be estimated that this is because the interaction between the ester group and the urethane group is good. Similarly, it can be presumed that the polyurea polymer dispersant is also good in the interaction between the ester group and the urea group.

The melting point of the pigment dispersant is preferably 20 ° C to 80 ° C, more preferably 30 ° C to 75 ° C. When the melting point is less than 20 ° C., the blocking property of the toner may be deteriorated, and when it exceeds 80 ° C., the low-temperature fixability may be deteriorated.
The amount of the pigment dispersant used in the present invention is preferably 1 part by mass or more and 100 parts by mass or less, and more preferably 5 parts by mass to 50 parts by mass with respect to 100 parts by mass of the pigment. When the addition amount is less than 1 part by mass with respect to 100 parts by mass of the pigment, the effect of addition is small, and the pigment may not be sufficiently dispersed and stabilized. In some cases, the quality of electrophotography is deteriorated and the cost is adversely affected, such as plasticizing the resin and deterioration of charging characteristics.

<Water-based granulation process>
The toner of the present invention is obtained by emulsifying or dispersing a solution or dispersion of a toner material in an aqueous medium and granulating it.
The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. The monomer, the polymer, the active hydrogen group-containing compound, and the active hydrogen It contains at least one of a polymer capable of reacting with a group-containing compound, a pigment and a pigment dispersant, and further contains other components such as a release agent (waxes) and a charge control agent as necessary.
The dissolved or dispersed liquid of the toner material preferably contains an organic solvent. That is, it is preferable to prepare the solution or dispersion by dissolving or dispersing the toner material in the organic solvent.
When the organic solvent is contained, the organic solvent is preferably removed during or after granulation of the toner.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is more. 80 to 120 parts by mass are more preferable.

(Aqueous medium)
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, the solvent miscible with water, these mixtures, etc. are mentioned. Among these, water is particularly preferable.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

(Emulsification or dispersion)
In the emulsification or dispersion of the toner material in the aqueous medium, it is preferable to disperse the toner material in the aqueous medium with stirring.
There is no restriction | limiting in particular as the method of the said dispersion | distribution, It can select suitably using a well-known disperser etc. Examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.

  When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 1,000 to 30,000 rpm is preferable, and 5,000 to 20,000 rpm is more preferable. In the case of a batch method, the dispersion time is preferably 0.1 to 5 minutes. As said dispersion temperature, 0-150 degreeC is preferable under pressure, and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

(Granulation)
The granulation is a method of granulating toner using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, and obtaining particles based on the adhesive substrate while producing an adhesive substrate described later. And a method of granulating the toner. Among these, a method of granulating toner while producing the adhesive base material is preferable.
The suspension polymerization method is an oil-soluble polymerization initiator, emulsification described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in a polymerizable monomer and a surfactant and other solid dispersant are contained. Emulsified and dispersed by the method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.

  Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, Particle surface of toner by partially using acrylate or methacrylate having amino groups such as methacrylamide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate Functional groups can be introduced into

  Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the surface of the toner particles to introduce a functional group.

  As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a pigment, a release agent, and the like are dispersed in an aqueous medium is prepared. After mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the particle surface of the toner by using a latex similar to the monomer that can be used in the suspension polymerization method.

In the method of granulating toner while producing the adhesive substrate, the toner material includes an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the granulation is carried out in an aqueous medium. Then, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to produce particles based on the adhesive base material while producing an adhesive base material.
The toner formed using such a granulation method includes an adhesive base material, and further contains other components such as a pigment, a pigment dispersant, a release agent, and a charge control agent, which are appropriately selected as necessary. Comprising.

(Pigment)
A known pigment can be used as the pigment used in the toner of the present invention. For example, carbon black, 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 lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phiise red, parachlor ortho nitroaniline red, risor fast scarlet G, brilliant fasts -Let, Brilliant Carmine BS, 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 red, polyazo red, chrome vermilion, benzidine orange, perinone oren , Oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue, bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and And mixtures thereof.

For example, when a copper phthalocyanine pigment and an aluminum phthalocyanine pigment are mixed and used during the production of toner particles, they are preferably mixed during the pigment production process in order to sufficiently bring out the characteristics of the respective pigments. Mixing by a pigment manufacturing process, particularly by solvent salt milling, is preferable in order to bring out the characteristics of each pigment and from the viewpoint of preventing contamination during pigment manufacturing.
The content of these pigments is usually 1 to 15 wt%, preferably 3 to 10 wt% with respect to the toner.

The pigment 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 master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, 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, Len-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, urethane, urea modified polyester, epoxy resin, epoxy polyol resin, polyurethane, Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. These can be used alone or in combination.

The master batch can be obtained by mixing and kneading the master batch resin and the above-described pigment under high shearing force to obtain a master batch.
At this time, an organic solvent can be used to enhance the interaction between the pigment and the resin.

  Also, a so-called flushing method called water flushing pigment aqueous paste is mixed and kneaded together with a resin and an organic solvent, the pigment is transferred to the resin side, and moisture and organic solvent components are removed. Therefore, it is not necessary to dry and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

(Adhesive substrate)
The adhesive base material exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

  The toner thus obtained contains a pigment and a pigment dispersant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

  The mass average molecular weight of the adhesive base material is preferably 3,000 or more, more preferably 5,000 to 1,000,000, and particularly preferably 7,000 to 500,000. When the mass average molecular weight is less than 3,000, the hot offset resistance may be lowered.

The glass transition temperature of the adhesive substrate is preferably 40 ° C to 65 ° C, and more preferably 45 ° C to 65 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 65 ° C., the low-temperature fixability may not be sufficient. Note that a toner containing a polyester resin subjected to a crosslinking reaction or an elongation reaction as an adhesive substrate has good storage stability even when the glass transition temperature is low.
Although the said adhesive base material is suitably selected according to the objective, a polyester-type resin etc. are used suitably.

  The binder resin precursor is not particularly limited and may be appropriately selected depending on the intended purpose. A modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably used.

  The modified polyester resin capable of reacting with the compound having an active hydrogen group is preferably a polyester having an isocyanate group as a polymer having reactivity with the active hydrogen group. In addition, you may form a urethane bond by adding alcohol when making the isocyanate group containing polyester resin and the compound which has an active hydrogen group react. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

  Specific examples of the adhesive substrate include a polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate, and bisphenol A ethylene oxide. A mixture of a 2-mole adduct and a polycondensate of isophthalic acid; a polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate; Mixtures of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthal Of a polyester prepolymer obtained by reacting a polycondensate of bisphenol A with isophorone diisocyanate with an isophorone diamine, and a polycondensate of bisphenol A ethylene oxide 2-mol adduct / bisphenol A propylene oxide 2-mol adduct and terephthalic acid Mixture: Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate, and bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate mixture; bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate converted to isophorone diisocyanate A mixture of a polyester prepolymer reacted with urea methylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid; a mixture of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid A mixture of a polyester prepolymer obtained by reacting a condensate with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate, urea-modified with ethylenediamine, Polyol prepolymer prepared by reacting bisphenol A ethylene oxide 2-mole adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate in urea with hexamethylenediamine Of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride A polyester prepolymer obtained by reacting a polycondensate with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2-mole adduct / bisphenol. A mixture of diol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate reacted with toluene diisocyanate in urea with hexamethylenediamine And a mixture of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate. In addition, 2 mol in the said bisphenol A ethylene oxide 2 mol adduct and the bisphenol A propylene oxide 2 mol adduct is an illustration, The thing of other numerical values (for example, 3 mol adduct etc.) may be used.

  The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having reactivity to the active hydrogen group undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.

  Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.

  The compound having an active hydrogen group can be appropriately selected according to the purpose. However, when the polymer having reactivity to the active hydrogen group is a polyester prepolymer having an isocyanate group, the compound has an elongation with the polyester prepolymer. Amines are preferred because they can be increased in molecular weight by reaction, crosslinking reaction or the like.

  The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Specifically, diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and these amino groups are blocked. Among them, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable. These may be used individually by 1 type and may use 2 or more types together.

Examples of the diamine include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
In addition, a reaction terminator can be used in order to stop the elongation reaction, the crosslinking reaction, and the like of the compound having an active hydrogen group and a polymer having reactivity with the active hydrogen group. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.
The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

The polymer having reactivity to active hydrogen groups (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, and can be selected from polyol resins, polyacrylic resins, polyester resins, and epoxy resins. And derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.
Examples of the functional group capable of reacting with the active hydrogen group of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, a functional group represented by the chemical structural formula -COC-, and the like, among which an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds.

  As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.

  The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.

  The polyol is not particularly limited and can be appropriately selected depending on the purpose. A diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, and the like can be used. A trihydric or higher alcohol mixture is preferred. These may be used individually by 1 type and may use 2 or more types together.

  Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkyne oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. The mixture of is particularly preferred.

  Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

  When a diol and a trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is preferably 0.01% by mass to 10% by mass, and 0.01% by mass to 1% by mass. Is more preferable.

  The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acids, trivalent or higher carboxylic acids, and mixtures of dicarboxylic acids and trivalent or higher carboxylic acids. A dicarboxylic acid or a mixture of a dicarboxylic acid and a small amount of a trivalent or higher polycarboxylic acid is preferred. These may be used alone or in combination of two or more.

Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4-20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.
As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are mixed and used, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is preferably 0.0% by mass to 10% by mass, and 0.01% by mass. % To 1% by mass is more preferable.

  As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

  The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 2% by mass to 20%. Mass% is particularly preferred. When the content is less than 0.5% by mass, the hot offset resistance is lowered, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability of the toner, and exceeds 40% by mass. In this case, the low-temperature fixability may be lowered.

  The polyisocyanate can be appropriately selected depending on the purpose, but it is blocked with an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an araliphatic diisocyanate, an isocyanurate, or the like, blocked with a phenol derivative, oxime, caprolactam, or the like. And the like.

Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used individually by 1 type and may use 2 or more types together.
When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.

  The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and 2% by mass. -20 mass% is still more preferable. When the content is less than 0.5% by mass, the hot offset resistance may be deteriorated, and when it exceeds 40% by mass, the low-temperature fixability may be deteriorated.

The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and still more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.
1000-30000 are preferable and, as for the mass average molecular weight of the polymer which has the reactivity with respect to an active hydrogen group, 1500-15000 are more preferable. When the mass average molecular weight is less than 1000, the heat-resistant storage stability may be lowered, and when it exceeds 30000, the low-temperature fixability may be lowered.

The said mass mean molecular weight can be calculated | required by measuring a tetrahydrofuran soluble part, for example using a gel permeation chromatography (GPC).
Here, the GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05 to 0.6% by mass is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the number of counts. As standard samples for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

In the present invention, the binder resin can be appropriately selected according to the purpose, and a polyester resin or the like can be used, but an unmodified polyester resin that is not modified is preferable. Thereby, low temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include a polycondensate of a polyol and a polycarboxylic acid. The unmodified polyester resin is partially compatible with the urea-modified polyester resin, that is, has a similar structure compatible with each other, in terms of low-temperature fixability and hot offset resistance. preferable.

  The mass average molecular weight of the unmodified polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 15,000. When the mass average molecular weight is less than 1,000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose said mass mean molecular weight is less than 1,000 is 8 mass%-28 mass%. On the other hand, if the mass average molecular weight exceeds 30,000, the low-temperature fixability may deteriorate.

The glass transition temperature of the unmodified polyester resin is preferably 30C to 70C, more preferably 35C to 60C, and still more preferably 35C to 55C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and still more preferably 20 mgKOH / g to 80 mgKOH / g. When the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 mgKOH / g to 50.0 mgKOH / g, and more preferably 1.0 mgKOH / g to 30.0 mgKOH / g. Thereby, the toner is easily negatively charged.

When the toner contains an unmodified polyester resin, the mass ratio of the polyester prepolymer having an isocyanate group to the unmodified polyester resin is preferably 5/95 to 25/75, more preferably 10/90 to 25/75. preferable. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.
In addition to the above components, the toner of the present invention can further contain a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.

(Release agent)
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, or paraffin wax and microcrystalline wax are especially excellent. From the viewpoint of preventing contamination of other members with wax, microcrystalline wax is more excellent.

  The melting point of the wax (release agent) is preferably 60 to 90 ° C. in the case of paraffin wax, and 70 to 100 ° C. is excellent in the case of microcrystalline wax. When the melting point of the wax is low, the wax volatiles increase, causing contamination to peripheral devices, and when the melting point is too high, the low-temperature fixing property is deteriorated and the manufacturability is deteriorated during production.

  The release agent has a melt viscosity of preferably 5 to 1000 cps, more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.

  The content of the release agent in the toner is preferably 40% by mass or less, and more preferably 3 to 30% by mass. When the content exceeds 40% by mass, the fluidity of the toner may be lowered.

(Charge control agent)
The charge control agent is not particularly limited and can be appropriately selected from known ones according to the purpose. It is preferable to use it. Specifically, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts including fluorine-modified quaternary ammonium salts, alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorosurfactant, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.

Commercially available products may be used as the charge control agent. Examples of commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, E-89 of phenol condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge of quaternary ammonium salt PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit) , Quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonia Polymer or the like having a functional group such as beam salts.
The charge control agent may be dissolved or dispersed after being melt-kneaded with the master batch, or may be dissolved or dispersed in a solvent together with each component of the toner, and may be fixed on the surface of the toner after the toner is produced. Also good.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified, but is 0.1% by mass to the binder resin. It is preferable that it is 10 mass%, and 0.2 mass%-5 mass% are more preferable. When the content is less than 0.1% by mass, the charge controllability may not be obtained. When the content exceeds 10% by mass, the chargeability of the toner becomes too large, and the electrostatic attractive force with the developing roller is low. May increase, resulting in a decrease in developer fluidity and a decrease in image density.

(Resin particles)
The resin particles are not particularly limited as long as they can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be thermoplastic resins. However, it may be a thermosetting resin. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used individually by 1 type and may use 2 or more types together.

  The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt eleminol RS-30 of methacrylic acid ethylene oxide adduct sulfate (manufactured by Sanyo Chemical Industries), divinylbenzene 1,6-hexanediol diacrylate and the like.

  The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

(Inorganic particles)
The inorganic particles are not particularly limited and can be appropriately selected from known materials according to the purpose. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, Strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate , Silicon carbide, silicon nitride and the like. These may be used individually by 1 type and may use 2 or more types together.

The primary particle diameter of the inorganic particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Further, BET specific surface area of the inorganic particles ^is preferably 20m ² / g~500m 2 / g.
The content of the inorganic particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 5.0% by mass.

(Fluidity improver)
A fluidity improver is an agent that increases surface hydrophobicity by surface treatment and prevents deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, and a fluoride are used. Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Silica, titanium oxide and the like are particularly preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

(Cleaning improver)
When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed. Specific examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm to 1 μm.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, and iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, a white magnetic material is preferable in terms of color tone.

<Toner production method>
Examples of the toner production method by the polymerization method include a method of forming toner particles while forming an adhesive substrate, which is shown below. In such a method, preparation of an aqueous medium phase, preparation of a liquid containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, a polymer having reactivity to active hydrogen groups And the synthesis of a compound having an active hydrogen group.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5% by mass to 10% by mass.
The liquid containing the toner material is prepared in a solvent by a compound having an active hydrogen group, a polymer having reactivity to the active hydrogen group, a pigment, a release agent, a pigment dispersant, a charge control agent, an unmodified polyester resin The toner material such as can be dissolved or dispersed.
In the toner material, components other than the polymer having reactivity with the active hydrogen group may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the toner material contains the toner material. When the liquid is added to the aqueous medium, it may be added to the aqueous medium.
The emulsification or dispersion of the toner material can be performed by dispersing a liquid containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base is formed by subjecting a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group to an extension reaction and / or a crosslinking reaction.
Adhesive substrates such as urea-modified polyester resins contain, for example, a liquid containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. It may be produced by emulsifying or dispersing together with a compound in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. It may be produced by emulsifying or dispersing in an added aqueous medium and by subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium, and after emulsifying or dispersing the liquid containing the toner material in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed on both from the particle interface in an aqueous medium. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having reactivity with active hydrogen groups and the compound having active hydrogen groups. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 150 ° C. or lower, and more preferably 40 ° C. to 98 ° C.
In a water-based medium, a method for stably forming a dispersion containing a polymer capable of reacting with an active hydrogen group such as a polyester prepolymer having an isocyanate group includes a reaction with an active hydrogen group in the aqueous medium phase. Examples include a method in which a liquid prepared by dissolving or dispersing a toner material such as a polymer, a pigment, a pigment dispersant, a release agent, a charge control agent, and an unmodified polyester resin in a solvent is added and dispersed by shearing force. It is done.

Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The number of rotations is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 150 ° C. or less, more preferably 40 ° C. to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 parts by mass to 2000 parts by mass, and more preferably 100 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the toner material. When the amount used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated and toner base particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the production cost is high. May be.

In the step of emulsifying or dispersing the liquid containing the toner material, a dispersing agent (emulsifying / dispersing agent) is used from the viewpoint of stabilizing the dispersion such as oil droplets and making the desired shape and sharpening the particle size distribution. It is preferable to use it.
The emulsifying / dispersing agent can be appropriately selected depending on the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, with surfactants being preferred. These may be used individually by 1 type and may use 2 or more types together.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and those having a fluoroalkyl group are preferably used. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (: carbon number 6 11 _(hereinafter referred to as such _C 6 ~C ₁₁₎₎ oxy] -1-alkyl _(C 3 -C ₄₎ sodium sulfonate, 3- [.omega.-fluoroalkanoyl _{(C 6 ~C} 8) -N- Ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C ₁₁ -C ₂₀ ) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (C ₇ -C ₁₃ ) or metal salt thereof, perfluoroalkyl (C ₄ -C ₁₂₎ sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N- Propyl-N-(2-hydroxyethyl) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{-C 10)} sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl _{(C 6 ~C} 10) -N- ethylsulfonyl glycine salts And monoperfluoroalkyl (C ₆ -C ₁₆ ) ethyl phosphate.

  Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (above, manufactured by Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC. -129 (manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (above, manufactured by Dainippon Ink Co., Ltd.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products, Inc.), footagent 100, 150 (above, manufactured by Neos), and the like.

Examples of the cationic surfactant include amine salt type surfactants such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, Quaternary ammonium salt type surfactants such as pyridinium salts, alkylisoquinolinium salts, benzethonium chloride and the like can be mentioned. Among these, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amino acids having a fluoroalkyl group, perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts, benzalkonium salts Benzethonium chloride, pyridinium salt, imidazolinium salt and the like are preferable. Commercially available cationic surfactants include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150, It is preferable to use F-824 (manufactured by Dainippon Ink); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.
Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include, for example, a monomer having a carboxyl group, an alkyl (meth) acrylate having a hydroxyl group, a vinyl ether, a vinyl carboxylate, an amide monomer, an acid chloride monomer, a monomer having a nitrogen atom or a heterocyclic ring thereof, etc. Homopolymers or copolymers obtained by polymerizing styrene, polyoxyethylene resins, celluloses and the like. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-hydroxy acrylate. Propyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. It is done. Specific examples of the vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, and the like. Examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Examples of the polyoxyethylene resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include ethylene lauryl phenyl ether, polyoxyethylene stearate phenyl, polyoxyethylene pelargonate phenyl, and the like. Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

When emulsifying or dispersing the toner material, a dispersant can be used as necessary.
Examples of the dispersant include acids such as calcium phosphate salts and those that are soluble in alkali. When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.
A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.
The obtained toner base particles may be mixed with particles such as a colorant, a release agent, and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used in this method, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (manufactured by Nara Machinery Co., Ltd.), Examples include a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), an automatic mortar, and the like.

The toner of the present invention can be used in various fields, but can be suitably used for image formation by electrophotography.
The volume average particle size of the toner of the present invention is preferably 3 μm to 8 μm, and more preferably 4 μm to 7 μm. When the volume average particle size is less than 3 μm, in the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be lowered. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. On the other hand, when the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter is large. May be.

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner of the present invention is preferably 1.00 to 1.25, and 1.05 to 1.25. More preferred. As a result, in the two-component developer, even if the toner balance for a long period of time is performed, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even in the case of long-term stirring in the developing device. . In the case of a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner on a member such as a blade for thinning the toner Therefore, even when the developing device is used (stirred) for a long time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase. is there.

  Here, the ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.). First, 0.1 to 5 ml of a surfactant such as an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of an electrolyte aqueous solution such as an approximately 1% by mass sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

The penetration of toner is preferably 15 mm or more, and more preferably 20 mm to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability is deteriorated.
Here, the penetration can be measured by a penetration test (JIS K2235-1991). Specifically, the toner is filled in a 50 ml glass container and left in a thermostatic bath at 50 ° C. for 20 hours, and then the toner is cooled to room temperature and a penetration test is performed. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

  The toner of the present invention preferably has a low fixing minimum temperature and a high offset non-occurrence temperature from the viewpoint of achieving both low-temperature fixability and offset resistance. For this purpose, it is preferable that the lower limit fixing temperature is less than 140 ° C. and the temperature at which no offset occurs is 200 ° C. or more. Here, the lower limit fixing temperature is the lower limit of the fixing temperature at which the residual ratio of the image density after a copy test using an image forming apparatus and rubbing the obtained image with a pad is 70% or more. The offset non-occurrence temperature can be obtained by measuring a temperature at which no offset occurs using an image forming apparatus adjusted to be developed with a predetermined amount of toner.

The thermal characteristics of the toner, also called flow tester characteristics, are evaluated as a softening temperature, an outflow start temperature, a 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
The softening temperature of the toner is preferably 30 ° C. or higher, and more preferably 50 ° C. to 90 ° C. When the softening temperature is less than 30 ° C., the heat resistant storage stability may be deteriorated.
The outflow start temperature of the toner of the present invention is preferably 60 ° C. or higher, and more preferably 80 ° C. to 120 ° C. When the outflow start temperature is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.
The 1/2 method softening point of the toner of the present invention is preferably 90 ° C. or higher, and more preferably 100 ° C. to 170 ° C. When the 1/2 method softening point is less than 90 ° C., the offset resistance may be deteriorated.

The glass transition temperature of the toner of the present invention is preferably 40 ° C to 70 ° C, and more preferably 45 ° C to 65 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. The glass transition temperature can be measured using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation).
The density of an image formed using the toner of the present invention is preferably 1.40 or more, more preferably 1.45 or more, and even more preferably 1.50 or more. If the image density is less than 1.40, the image density may be low and high image quality may not be obtained. The image density was determined by using a tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), setting the surface temperature of the fixing roller to 160 ± 2 ° C., and developing the copy paper type 6200 (produced by Ricoh Co., Ltd.). A solid image having an adhesion amount of 1.00 ± 0.1 mg / cm ² was formed, and the image density at any five locations in the obtained solid image was measured using a spectrometer 938 spectrodensitometer (manufactured by X-Light Corporation). ), And the average value can be calculated.

  The color of the toner of the present invention can be appropriately selected according to the purpose, and can be one or more selected from the group consisting of black toner, cyan toner, magenta toner, and yellow toner. It can be obtained by appropriately selecting a colorant.

(Developer)
The developer of the present invention contains the toner of the present invention and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.

When the developer of the present invention is used as a two-component developer, even if the toner balance is maintained over a long period of time, there is little fluctuation in the particle diameter of the toner. An image is obtained.
Although the said carrier can be suitably selected according to the objective, what has a core material and the resin layer which coat | covers a core material is preferable.
The material of the core material can be appropriately selected from known materials, and examples thereof include manganese-strontium-based materials and manganese-magnesium-based materials of 50 emu / g to 90 emu / g. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.
The volume average particle diameter of the core material is preferably 10 μm to 150 μm, and more preferably 40 μm to 100 μm. When the volume average particle diameter is less than 10 μm, fine powder increases in the carrier, magnetization per particle may decrease and carrier scattering may occur, and when it exceeds 150 μm, the specific surface area decreases, Toner scattering may occur, and in the case of full color with many solid portions, reproduction of the solid portions may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, polyhalogenated olefins, polyester resins Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetra Examples include fluoroterpolymers such as copolymers of fluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene-based resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve etc. are mentioned. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. If the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. If the content exceeds 5.0% by mass, the resin layer is thick and the carrier Fusion may occur between them, and the uniformity of the carrier may decrease.
The content of the carrier in the two-component developer is preferably 90% by mass to 98% by mass, and more preferably 93% by mass to 97% by mass.
The developer of the present invention can be used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

(Toner container)
The toner-containing container of the present invention has the toner of the present invention. The toner-containing container of the present invention includes the case of having the developer of the present invention.
The container of the toner container can be appropriately selected from known ones, and those having a container body and a cap are preferably used.
The size, shape, structure, material and the like of the container body can be appropriately selected according to the purpose. The shape is preferably cylindrical or the like, and preferably has spiral irregularities formed on the inner peripheral surface, and part or all of the spiral portion has a bellows function. By rotating such a container main body, the toner as the contents can be transferred to the discharge port side.
The material of the container body is preferably a material with good dimensional accuracy, and examples thereof include resins such as polyester resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention can be easily stored and transported, has excellent handleability, and can be removably attached to a process cartridge, an image forming apparatus or the like to supply toner.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means. In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes 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 step, a cleaning step. , Including recycling process, control process, etc.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (hereinafter, also referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is particularly limited in terms of material, shape, structure, size, and the like. However, it can be suitably selected from known ones, and the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, polysilane, phthalopolymethine and the like. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.

The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with the transfer charger using the visible image, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
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 preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram showing a configuration of an embodiment of the image forming apparatus according to the present invention. In the figure, reference numeral 100 denotes a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.
In the copying apparatus main body 100, four image forming means 18 each provided with various means for performing an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as an electrostatic latent image carrier. A tandem type image forming apparatus 20 is provided. Above the tandem image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoconductor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto the transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 252 against a fixing belt 254 which is an endless belt.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .
The developing device 4 of the image forming unit 18 uses a developer containing the above toner. In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.
In addition, the photosensitive member 40 and the developing device are integrally supported, and the process cartridge can be formed to be detachable from the main body of the image forming apparatus. In addition, the process cartridge may include a charging unit and a cleaning unit.

FIG. 3 is a schematic view showing a configuration including a fixing belt as an embodiment of the fixing device of the present invention. The fixing device 25 is a heating roller 253, a fixing roller 251, a pressure roller 252 that is a pressure unit that comes into pressure contact with the fixing roller 251, and a fixing unit that is stretched between the heating roller 253 and the fixing roller 251. And a fixing belt 254.
The fixing roller 251 and the pressure roller 252 are provided with an elastic layer made of a heat-resistant elastic material on the outer periphery of a metal cored bar in substantially the same manner as the fixing roller 251 and the pressure roller 252 of the fixing device 25 shown in FIG. . The thickness of the elastic layer is adjusted as appropriate. Further, a release layer made of a fluorine-based resin or the like is provided on the surface layer of the elastic layer in order to improve the release property of the transfer paper and toner. A halogen heater is disposed inside each of the core bars. The pressure roller 253 is pressed against the fixing roller 251 with a fixing belt 254 interposed therebetween by a pressure member such as a spring (not shown), and is fixed between the fixing roller 251 by deforming the elastic layer. Form a nip where the toner can be pressed and heated for a long time.
The fixing belt 254 is made of an endless belt-like substrate made of heat-resistant resin or metal. Examples of the material of the heat resistant resin include polyimide, polyamideimide, polyether ether ketone, and examples of the material of the metal belt include nickel, aluminum, and stainless steel. A resin and a multilayer may be formed. In particular, a belt obtained by electroforming nickel on a polyimide resin is preferable because it has strength and elasticity and is durable. The thickness is preferably 100 μm or less. Since the fixing belt 254 is in pressure contact with transfer paper and toner, the fixing belt 254 has an elastic layer made of high-release silicone rubber or the like and a heat-resistant release layer made of a fluorine resin having a small friction coefficient.
The heating roller 253 is a member that stretches the fixing belt 254 that is being stretched and further heats it. For this reason, a heat source such as a halogen lamp or a nichrome wire is provided inside the heating roller 253. The heating roller 253 is a thin-walled roller of a hollow metal cylinder such as aluminum, carbon steel, stainless steel, etc., but by using an aluminum cylinder having a thickness of 1 to 4 mm with good thermal conductivity, The temperature distribution can be reduced. Further, the surface of the heating roller 253 is subjected to alumite treatment in order to prevent abrasion with the fixing belt 254.
A temperature sensor 255 that includes a thermocouple, a thermistor, and the like and detects the temperature of the outer peripheral surface of the fixing belt 254 is disposed on the outer peripheral surface of the heating roller 253 with the fixing belt 254 interposed therebetween. In response to a detection signal from the temperature sensor, the operation of the heater inside the heating roller 253 and the like is controlled by a temperature control device (not shown).

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the other contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. The document is placed in the reading sensor 36 and the original content is read.
When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer belt 10 is rotated and conveyed. To do. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer belt 10, the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt 10.
On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, so Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 50 is rotated to feed out the sheets on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped.
Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer belt 10, the sheet is fed between the intermediate transfer belt 10 and the secondary transfer device 22, and is transferred by the secondary transfer device 22. A color image is recorded on the sheet.
The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching roller 55 is used to switch the discharge image. The paper is discharged at 56 and stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56.
On the other hand, the intermediate transfer belt 10 after the image transfer is removed by the intermediate transfer belt cleaning device 17 to remove residual toner remaining on the intermediate transfer belt 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for the image formation again.
Since the image forming apparatus, the image forming method, and the process cartridge according to the present invention use the toner according to the present invention, it is possible to form clearer image quality with plain paper than with offset printing.

Hereinafter, the toner of the present invention will be described with reference to examples, but the present invention is not limited to the following examples and should not be construed. In Examples, “part” and “%” in each example are based on mass, and “mol” means molar ratio.
The “acid value and amine value”, “melting point of wax”, “mass average molecular weight of resin”, and “volume average particle diameter of toner” described below were measured as follows.

<Measurement of acid value and amine value>
Here, the acid value (AV) and the amine value are specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value and amine value-
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation was performed as follows.
Titration was carried out with N / 10 caustic potash-alcohol solution that had been standardized in advance, and the acid value was determined from the consumption of alcohol potash solution by the following formula.
Acid value = KOH (ml) x N x 56.1 / sample mass (N is a factor of N / 10 KOH)

-Method for measuring amine value-
Sample preparation: 0.5 g of toner was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated by the above-described apparatus, but specifically, it was determined as follows.
Titration was carried out with a pre-standardized N / 10 hydrochloric acid-alcohol solution, and the amine value was determined from the consumption of hydrochloric acid-alcohol solution.

<Measurement of melting point (Tm) of wax>
The softening point (Tm) of the wax is determined by the peak top indicating the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC). Moreover, the measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
-Measurement conditions-
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C. around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature rise, and obtains the peak temperature using the peak analysis function of the analysis software. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the melting point (Tm) of the wax.

<Measurement of mass average molecular weight of resin>
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 ml / min
Sample: 0.4 ml of 0.15% sample was injected Sample pretreatment: Toner was dissolved in tetrahydrofuran THF (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15%, and then filtered through a 0.2 μm filter. The filtrate is used as a sample. 100 μl of the THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
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.

<Number average molecular weight (Mn)>
For the number average molecular weight and the weight average molecular weight, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured from the molecular weight distribution by gel permeation chromatography (GPC) of the tetrahydrofuran-soluble matter.
Specifically, the column was stabilized in a 40 ° C. heat chamber, tetrahydrofuran as a column solvent at this temperature was flowed at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement was performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ^5. 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 48 × 10 ⁶ (manufactured by Toyo Soda Kogyo Co., Ltd.), and at least about 10 standard polystyrene samples were used. An RI (refractive index) detector was used as the detector.

<Volume average particle diameter of toner>
The volume average particle diameter (Dv) of the toner is measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm and analyzed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). went. Specifically, 0.5 ml of 10% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and 0.5 g of each toner is added. The mixture was stirred, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II; manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Toner Shape Factor SF-1>
The toner shape factor SF-1 was obtained by randomly sampling 300 SEM images of toner obtained by measurement with an FE-SEM (S-4200) manufactured by Hitachi, Ltd., and using the image information via Nireco Corporation. The sample was introduced into an image analyzer (Luzex AP) and analyzed, and the value obtained from the following equation was defined as SF-1. The value of SF-1 is preferably a value obtained by Luzex, but is not particularly limited to the FE-SEM device and the image analysis device as long as a similar analysis result can be obtained.
SF-1 = (L ² / A) × (π / 4) × 100
Here, L is the absolute maximum length of the toner, and A is the projected area of the toner.
If it is a true sphere, it will be 100, and it will change from spherical to indefinite as the value becomes larger than 100. In particular, SF-1 is a shape factor indicating the shape (ellipse, sphere, etc.) of the entire toner.

(Synthesis Example 1)
-Synthesis of Pigment Dispersant A-
In a 4-neck 500 ml separable flask equipped with a stirrer, dropping funnel, reflux condenser, gas inlet tube, and thermometer, 8 parts of dimethylolbutanoic acid, N, N-bis (2-hydroxypropyl) aniline 24 And 60 parts of methyl ethyl ketone were charged, the inside of the flask was replaced with dry nitrogen, and the temperature was raised to 80 ° C. with stirring. Under stirring, 62 parts of isophorone diisocyanate was added dropwise over 10 minutes and allowed to react for 6 hours. The reaction product was cooled to 65 ° C., 319 parts of water and 11 parts of 25% ammonia water were added, the temperature was raised, and 60 parts of methyl ethyl ketone as a solvent and 330 parts of alkaline water were removed. Thus, Pigment Dispersant A having a melting point of 65 ° C., an acid value of 0.2 mgKOH / g, and an amine value of 0.3 mgKOH / g was produced.

(Synthesis Example 2)
-Synthesis of unmodified polyester resin A-
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin 2 parts of oxide was added and reacted at 230 ° C. under normal pressure for 8 hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize unmodified polyester resin A. did.
The obtained unmodified polyester resin A had a number average molecular weight of 2500, a mass average molecular weight of 6700, a glass transition temperature of 44 ° C., and an acid value of 25 mgKOH / g.

(Synthesis Example 3)
-Synthesis of Pigment Dispersant B-
In a 4-neck 500 ml separable flask equipped with a stirrer, dropping funnel, reflux condenser, gas inlet tube, and thermometer, 8 parts of dimethylolbutanoic acid, N, N-bis (2-hydroxypropyl) aniline 24 And 60 parts of methyl ethyl ketone were charged, the inside of the flask was replaced with dry nitrogen, and the temperature was raised to 80 ° C. with stirring. Under stirring, 62 parts of isophorone diisocyanate was added dropwise over 10 minutes and reacted for 4 hours. The reaction product was cooled to 65 ° C., 319 parts of water and 11 parts of 25% ammonia water were added, the temperature was raised, and 60 parts of methyl ethyl ketone as a solvent and 330 parts of alkaline water were removed. Thus, Pigment Dispersant B having a melting point of 65 ° C., an acid value of 0.2 mgKOH / g, and an amine value of 0.3 mgKOH / g was produced.

(Synthesis Example 4)
-Synthesis of Pigment Dispersant C-
In a 4-neck 500 ml separable flask equipped with a stirrer, dropping funnel, reflux condenser, gas inlet tube, and thermometer, 8 parts of dimethylolbutanoic acid, N, N-bis (2-hydroxypropyl) aniline 24 And 60 parts of methyl ethyl ketone were charged, the inside of the flask was replaced with dry nitrogen, and the temperature was raised to 80 ° C. with stirring. Under stirring, 62 parts of isophorone diisocyanate was added dropwise over 10 minutes and allowed to react for 12 hours. The reaction product was cooled to 65 ° C., 319 parts of water and 11 parts of 25% ammonia water were added, the temperature was raised, and 60 parts of methyl ethyl ketone as a solvent and 330 parts of alkaline water were removed. Thus, Pigment Dispersant C having a melting point of 65 ° C., an acid value of 0.2 mgKOH / g, and an amine value of 0.3 mgKOH / g was produced.

[Example 1]
(Preparation of Toner 1)
-Preparation of pigment dispersion A-
In a container in which a stir bar was set, 250 parts of unmodified polyester resin A, 100 parts of pigment dispersant A, and 1625 parts of ethyl acetate were charged and stirred until the unmodified polyester resin was dissolved. Next, 250 parts of a magenta pigment CIPigmentRed269 (Permanent Carimine 3810 manufactured by Sanyo Dyeing Co., Ltd.) was added to the container and stirred for 1 hour to obtain a pigment mixed solution.
The obtained pigment mixed solution was filled with 80% by volume of 0.3 mm zirconia beads using an ultra visco mill (made by Imex Co., Ltd.), a liquid feed speed of 1 kg / hour, and a disk peripheral speed of 8 m / second. The pigment dispersion A was prepared by performing 5 passes under conditions.

-Preparation of raw material solution-
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of unmodified polyester resin A, 110 parts of paraffin wax (HNP-9 melting point 75 ° C., Nippon Seiwa Co., Ltd.), salicylic acid metal complex E-84 (Orient Chemical Co., Ltd.) (Company) 22 parts and ethyl acetate 947 parts were charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour to obtain a raw material solution.
The obtained raw material solution is transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour and a disk peripheral speed of Carnauba wax (melting point: 80 to 86 ° C.) was dispersed by three passes under the condition of 6 m / sec to obtain a wax dispersion.
Next, a wax dispersion and 290 parts of pigment dispersion A were added to 1324 parts of a 65% ethyl acetate solution of unmodified polyester resin A. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 30 minutes to obtain a dispersion of toner material.
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, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2100, a mass average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. A prepolymer was synthesized. The resulting prepolymer had a free isocyanate content of 1.53%.
In a reaction vessel equipped with a stirring bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction container, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (made by Tokushu Kika Co., Ltd.). An oil phase mixture was obtained.
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries, Ltd.), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain an emulsion.
The obtained emulsion was heated, heated to 75 ° C., and reacted for 5 hours. Next, 30 parts of a 1% by mass ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.

-Production of aqueous media-
990 parts of water, 83 parts of a resin particle dispersion, 37 parts of a 48.5% aqueous solution Eleminol MON-7 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) of sodium dodecyl diphenyl ether disulfonate, 1% aqueous solution serogen BS of polymer dispersant sodium carboxymethylcellulose -H (Daiichi Kogyo Seiyaku Co., Ltd.) 135 parts and ethyl acetate 90 parts were mixed and stirred to obtain an aqueous medium.

-Preparation of toner-
To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration.
To the obtained filter cake, 10% hydrochloric acid was added to adjust the pH to 2.8, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer and then filtered.
Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain toner base particles. The obtained toner base particles had a volume average particle size of 5.7 μm.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide are added as external additives and mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The toner 1 was prepared by processing. The evaluation of toner 1 is shown in Table 1.

[Example 2]
(Preparation of Toner 2)
Toner 2 was produced in the same manner as in Example 1 except that the magenta pigment in Pigment Dispersion A was changed to Cyanine Blue 4920 manufactured by Dainichi Seika Kogyo. The evaluation of toner 2 is shown in Table 1.

Example 3
(Preparation of Toner 3)
In the pigment dispersion A, the magenta pigment is C.I. I. Toner 3 was produced in the same manner as in Example 1 except that Pigment Yellow 74 (Sico Yellow FR 1252 manufactured by BASF) was used. The evaluation of toner 3 is shown in Table 1.

Example 4
(Preparation of Toner 4)
A toner 4 was produced in the same manner as in Example 1, except that the preparation of the pigment dispersion was changed to “-preparation of a pigment dispersion” described below. The evaluation of toner 4 is shown in Table 1.
-Preparation of pigment dispersion-
1200 parts of water, 360 parts of copper phthalocyanine pigment, 72 parts of pigment dispersant A, and 540 parts of unmodified polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.
500 parts of the master batch and 1625 parts of ethyl acetate were charged and stirred until dissolved to prepare a pigment dispersion.

Example 5
A toner was prepared in the same manner as in Example 1 except that the pigment dispersant A was changed to the pigment dispersant B. The evaluation of toner 5 is shown in Table 1.

Example 6
A toner was prepared in the same manner as in Example 1 except that the pigment dispersant A was changed to the pigment dispersant C. The evaluation of toner 6 is shown in Table 1.

[Comparative Example 1]
(Preparation of Toner 5)
In the pigment dispersion A, except that the pigment dispersant A was changed to a polyester pigment dispersant (Disparon DA-725, manufactured by Enomoto Kasei Co., Ltd., acid value 20 mgKOH / g, amine value 40 mgKOH / g, melting point 36 ° C.). In the same manner as in Example 1, a toner 5 was produced. The evaluation of toner 7 is shown in Table 1.

[Comparative Example 2]
(Production of Toner 6)
Implementation was performed except that the pigment dispersant A was changed to a polyester pigment dispersant (Disparon DA-725, manufactured by Enomoto Kasei Co., Ltd., acid value 20 mgKOH / g, amine value 40 mgKOH / g, melting point 36 ° C.) in the pigment dispersion A. In the same manner as in Example 2, toner 6 was produced. The evaluation of toner 8 is shown in Table 1.

[Comparative Example 3]
(Preparation of Toner 7)
Implementation was performed except that the pigment dispersant A was changed to a polyester pigment dispersant (Disparon DA-725, manufactured by Enomoto Kasei Co., Ltd., acid value 20 mgKOH / g, amine value 40 mgKOH / g, melting point 36 ° C.) in the pigment dispersion A. In the same manner as in Example 3, toner 7 was produced. The evaluation of toner 9 is shown in Table 1.

<Color characteristic evaluation>
Evaluation was performed using a tandem type image forming apparatus (Imagio Neo 450 manufactured by Ricoh Co., Ltd.) equipped with a belt heating fixing device shown in FIG. In the belt heat fixing apparatus, the belt substrate is 100 μm thick polyimide, the intermediate elastic layer is 100 μm thick silicone rubber, the surface anti-offset layer is 15 μm thick PFA, the fixing roller is silicone foam, and the pressure roller metal cylinder. Was made of SUS with a thickness of 1 mm, a pressure roller with an offset prevention layer of PFA tube + silicone rubber with a thickness of 2 mm, a heating roller with a thickness of 2 mm, and a surface pressure of 1 × 10 ⁵ Pa.

The toner fixed image was prepared as follows. Ricoh full-color PPC paper TYPE6000 <70W> A4 size T (manufactured by Ricoh Co., Ltd.) was used for the creation of the fixed image. The evaluation was performed at a toner adhesion amount of 0.3 mg / cm ² and a fixing temperature of 160 ° C. The 60 ° gloss at that time was 5 to 15.
The obtained fixed image was evaluated for color reproducibility (color value). The color reproducibility was evaluated by measuring CIE L *, a *, and b * of the fixed image. Specifically, based on ISO / CD13655, it measured using the X-Rite color difference meter 938 Spectrodentitometer (measurement light source CIE-D65).
From this, the color difference by the L * a * b * color system was determined by the following formula (1) (JIS Z8730), and the saturation was determined by the following formula (2) (JIS Z8729).
Equation (1) is, ΔE * ab = [(ΔL *) 2 + (Δa *) 2 + (Δb *) 2] ^1/2. Here, ΔE * ab represents a color difference according to the L * a * b * color system, and ΔL *, Δa *, and Δb * are non-delivery in the L * a * b * color system defined in JIS Z8729. The difference between the CIE lightness L * and the color coordinates a * and b * of the object color. The standard color used was the art paper standard color described in the ISO / Japan Color offset sheet-like printing color standard Japan Color color reproduction printing 2001 manual. Generally, when ΔE * ab is 3 or more, it is recognized that there is a color difference when viewed by a person.
Formula (2) is C * ab = [(a *) ² + (b *) ² ] ^1/2 .
The coloring power of the toner was measured by measuring the density of the fixed image using a color difference meter 938 Spectrodentometer (measurement light source CIE-D65) manufactured by X-Rite.

From the results in Table 1, it was found that the toners of Examples 1 to 6 were excellent in saturation, coloring power, and hue difference.
On the other hand, since the toners of Comparative Examples 1 to 3 have insufficient pigment dispersibility, the color characteristics of the toner were deteriorated.

It is the schematic which shows an example of the process cartridge of this invention. 1 is a schematic explanatory diagram illustrating an example of an image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration including a fixing belt as an embodiment of a fixing device used in the present invention.

Explanation of symbols

10 Intermediate transfer belt (intermediate transfer member)
18 Image forming means 21 Exposure device 25 Fixing device 40 Photoconductor (electrostatic latent image carrier)
22 Secondary transfer device 62 Primary transfer means 100 Copying device main body 101 Photoconductor 102 Charging means 103 Exposure by exposure means 104 Development means 105 Recording medium 107 Cleaning means 108 Transfer means 200 Paper feed table 251 Fixing roller 252 Pressure roller 253 Heating roller 254 Fixing belt 255 Application roller 256 Fixing roller cleaning roller 257 Pressure roller cleaning roller 258 Temperature sensor 300 Scanner 400 Automatic document feeder

Claims (14)

A toner material containing at least a binder resin, a pigment, and a pigment dispersant;
The pigment dispersant contains a polyurea pigment dispersant,
The pigment dispersant has an acid value of 0.01 mgKOH / g or more and 1 mgKOH / g or less, and an amine value of 0.01 mgKOH / g or more and 1 mgKOH / g or less. A toner characterized by being dispersed or emulsified into a granule. The toner according to claim 1, wherein the melting point of the pigment dispersant is 20 ° C. to 80 ° C. The toner according to claim 1 or 2 , wherein the content of the pigment dispersant is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. The toner according to claim 1 wherein the toner material, characterized in that it further comprises a wax. The toner according to claim 4 , wherein the wax is paraffin wax. The toner according to claim 4 , wherein the wax is a microcrystalline wax. The toner according to claim 4 , wherein the wax has a melting point of 60 ° C. to 100 ° C. The toner according to any one of claims 4 to 6 , wherein the wax has a melting point of 70C to 90C. A dispersion containing a binder resin precursor made of a modified polyester resin and an oil phase to which a fine particle dispersant is added are introduced into an aqueous medium, and the binder resin precursor and a compound that extends or crosslinks are dissolved. , claim 1 of the oil phase and emulsified dispersion is dispersed in the aqueous medium, wherein the binder resin precursor in an emulsion dispersion by crosslinking or elongation reaction, characterized in that it is granulated The toner according to any one of 8 . The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and the shape factor SF-1 of the toner is 110 to 150. The toner according to claim 1 , wherein the toner is a toner. Developing agent characterized by containing the toner according to any one of claims 1 to 10. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image An image forming method including at least a transfer step of transferring the image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium,
The toner, image forming method which is a toner according to any one of claims 1 to 10. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image An image forming apparatus having at least developing means for transferring, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium,
The toner, image forming apparatus which is a toner according to any one of claims 1 to 10. The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A removable process cartridge,
Process cartridge the toner is characterized in that it is a toner according to any one of claims 1 to 10.

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