JP4295144B2 - Toner and method for producing the same, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a manufacturing method thereof, a developer using the toner, a container containing a toner, a process cartridge, an image forming apparatus, and The present invention relates to an image forming method.

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1, Patent Document 2, and Patent Document 3). The fixing method in the electrophotographic method is a heat roller fixing method in which a heat roller is directly pressed against a toner image on a transfer material and fixed because it is excellent in thermal efficiency and can be downsized. Is widely used.

In the fixing step, the recording member is sandwiched between a pair of roller-shaped or belt-shaped fixing members each having a heater therein, and the toner is heated and melted and fixed on the recording member by applying pressure. At this time, if the heating temperature is too high, the toner is excessively melted and a problem (hot offset) of fusing to the fixing member occurs. On the other hand, if the heating temperature is too low, there is a problem that the toner is not sufficiently melted and fixing becomes insufficient. From the viewpoint of energy saving and downsizing of an image forming apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required. In addition, it is necessary that the toner does not block (blocking resistance) during storage and at ambient temperature in the apparatus.
In particular, in full-color copying machines and full-color printers, the gloss and color mixing properties of the image are required, so the toner needs to have a lower melt viscosity, and a sharp-melt polyester toner binder is used. ing. In such a toner, hot offset is likely to occur. Therefore, in a full-color device, conventionally, silicone oil or the like is applied to a fixing member. However, in order to apply silicone oil to the fixing member, an oil tank and an oil application device are required, and the device becomes complicated and large. In addition, the fixing member is deteriorated, and maintenance is required every certain period. Further, it is inevitable that oil adheres to copy paper, OHP (overhead projector) film, and the like, especially in OHP, there is a problem that the color tone is deteriorated by the adhered oil.

Therefore, a method of adding wax to the toner (oilless fixing) is generally used in order to prevent the toner from fusing without applying oil to the fixing member. However, the mold release effect is greatly influenced by the dispersion state of the wax in the binder.
In conventional kneading / pulverizing toner, waxes are finely dispersed by shearing force during kneading. On the other hand, in a method for producing toner in which an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form toner particles in an aqueous medium, toner particles are formed. After the polyester resin and ethyl acetate are dissolved by heating, the wax particles precipitated by cooling are finely dispersed by wet grinding.
However, in this case, the synthetic ester wax is excellent in hot offset property during fixing and wrapping around the fixing belt, but it is difficult to finely disperse by wet pulverization, the viscosity of the wax dispersion becomes high, and the productivity decreases. There is a problem of end up.

  Therefore, it is excellent in various properties such as hot offset property during fixing and wrapping property to a fixing member, improves the manufacturability, achieves both low temperature fixability and color reproducibility, and obtains a high image quality toner and its efficient The manufacturing method and the related technology using the toner are not yet provided.

US Pat. No. 2,297,691 Japanese Patent Publication No.42-23910 Japanese Patent Publication No.43-24748

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, the present invention is excellent in various properties such as hot offset at fixing and wrapping around a fixing belt, improved in manufacturability, compatible with both low-temperature fixing and color reproducibility, and a toner capable of obtaining high image quality. An object of the present invention is to provide a manufacturing method thereof, a developer using the toner, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

Means for solving the problems are as follows. That is,
<1> Adhesive base material obtained by dispersing and reacting in an aqueous medium an organic solvent phase in which an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound and a wax dispersion are dissolved or dispersed. An adhesive base material producing step for obtaining a toner while producing a toner, and a wet grinding step for preparing at least a wax dispersion by wet grinding a synthetic ester wax and a plant wax, and the solvent of the wax dispersion is a solvent Ethyl acetate, and the synthetic ester wax is a wax synthesized from any of pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, and pentaerythritol tetrabehenate, Ester wax is characterized by being carnauba wax. It is a method for producing a toner.
<2> synthetic ester wax The method for producing a toner according to <1> is a branched type.
<3> The toner according to any one of <1> to <2>, wherein a mixing mass ratio of the synthetic ester wax to the plant wax (synthetic ester wax: plant wax) is 1: 0.1 to 10 . It is a manufacturing method .
<4> The method for producing a toner according to any one of <1> to < 3 >, wherein the adhesive base material includes a polyester resin.
<5> The toner production method according to < 4 >, wherein the polyester resin includes a urea-modified polyester resin.
<6> The toner production method according to any one of < 1 > to <5>, wherein the wax dispersion has a viscosity at 25 ° C. of 1500 cp or less .

  The toner of the present invention is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. Synthetic ester wax and vegetable wax are contained. Since the toner includes the adhesive base obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, the toner has anti-aggregation property, chargeability, and fluidity. Excellent properties such as transferability and fixability. Further, a synthetic ester wax excellent in hot offset property and wrapping property at the time of fixing and a plant wax having a low viscosity of the dispersion obtained by wet pulverization in a short time and excellent in productivity are used in combination. As a result, it has excellent properties such as anti-aggregation, charging, fluidity, transferability, and fixability, excellent properties such as hot offset during fixing, and wrapping properties with respect to the fixing belt, and improved productivity. Both low-temperature fixability and color reproducibility are compatible, and high image quality can be obtained.

  In the toner production method of the present invention, an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and the crystalline polyester resin dispersion are dispersed and reacted in an aqueous medium. It includes an adhesive base material generation step for obtaining toner while generating an adhesive base material, and a wet pulverization step. In the method for producing the toner, in the adhesive base material producing step, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are dispersed and reacted in the aqueous medium to obtain a toner. Generated. Since the toner includes the adhesive base obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, the toner has anti-aggregation property, chargeability, and fluidity. Excellent properties such as transferability and fixability. In the wet pulverization step, a combination of a synthetic ester wax excellent in hot offset property and wrapping property at the time of fixing and a plant wax excellent in manufacturability with a low viscosity of the dispersion obtained by wet pulverization Is finely dispersed by wet pulverization. As a result, it has excellent properties such as anti-aggregation, charging, fluidity, transferability, and fixability, excellent properties such as hot offset during fixing, and wrapping properties with respect to the fixing belt, and improved productivity. Both low-temperature fixability and color reproducibility are compatible, and high image quality can be obtained.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, both low-temperature fixability and color reproducibility are achieved, and high image quality is obtained.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when image formation is performed by electrophotography using the toner contained in the toner-containing container, both low-temperature fixability and color reproducibility can be achieved, and high image quality can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is attachable to and detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that both low-temperature fixability and color reproducibility can be achieved and a clear image quality can be obtained.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, both low-temperature fixability and color reproducibility can be achieved, and high image quality can be obtained.

  The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, the low-temperature fixability and the color reproducibility can be balanced with each other, and a clear high-quality image can be formed.

  According to the present invention, a toner that can solve various problems in the past, is excellent in various properties such as hot offset at fixing and wrapping around a fixing belt, is improved in manufacturability, and has both low-temperature fixability and color reproducibility. Is obtained.

(toner)
The toner of the present invention is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. It contains a synthetic ester wax and a vegetable wax, and further contains other components such as a colorant, resin fine particles, a non-reactive polyester resin, and a charge control agent as necessary.

-Adhesive substrate-
The adhesive substrate is a polymer obtained 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 other binders appropriately selected from known binder resins as necessary.

The weight average molecular weight of the adhesive substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, 1,000 or more is preferable, and 2,000 to 10,000,000 is more preferable. 3,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 30 ° 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.

There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester-type resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophoronediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol Polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A Polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and ureaated with hexamethylenediamine, a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (9) bisphenol A ethylene Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer urea-modified with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and isophthalic acid with toluene diisocyanate with urea methylenediamine, a 2-mole adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, 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 heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And those obtained by reacting the active hydrogen group-containing polyester resin with polyisocyanate (PIC).

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and the like. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
As said aromatic polycarboxylic acid, a C9-C20 thing is preferable, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
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 cell solves include methyl cell solve. 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.

-Release agent-
As the mold release agent, a synthetic ester wax and a plant-based wax are used in combination, and further contain other waxes as necessary.

  The synthetic ester wax is an ester compound obtained from carboxylic acid and alcohol. As the carboxylic acid, a higher fatty acid having 13 to 30 carbon atoms is used. As the alcohol, an alcohol having 2 to 30 carbon atoms is preferably used, and a branched synthetic ester wax using a 3-6 valent polyhydric alcohol is preferably used.

Examples of the higher fatty acid include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, and the like.
Examples of the monohydric alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, and triacontanol.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,10-decanediol. 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, diethylene glycol Propylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiro glycol, 1,4-phenylene glycol, bisphenol A, hydrogenated bisphenol A, etc. Can be mentioned.
Examples of the trivalent alcohol include 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,4-butanetriol, glycerin, 2-methylpropanetriol, tri Examples include methylolethane, triethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
Examples of the tetravalent alcohol include 1,2,3,6-hexanetetrol, pentaerythritol, and the like. Examples of the pentavalent alcohol include glucose and the like. Examples of the hexavalent alcohol include dipentaerythritol.
The branched type synthetic ester wax is preferable in terms of high releasability, but pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, and the like are particularly preferable.

  Examples of the plant-based wax include carnauba wax, castor oil, rapeseed oil, soybean oil, wood wax, cotton wax, rice wax, sugarcane wax, candelilla wax, Japan wax, jojoba oil, and the like. Of these, carnauba wax is particularly preferable because of its excellent dispersibility.

The mixing mass ratio of the synthetic ester wax and the plant wax (synthetic ester wax: plant wax) is preferably 1: 0.1 to 10, and more preferably 1: 0.5 to 5.
If the ratio of the synthetic ester wax is too large, fine dispersion by wet pulverization may be difficult, and if it is too small, the hot offset property at the time of fixing and the winding property to the fixing member may be poor.

  Examples of the other waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, and natural waxes.

  Examples of the synthetic hydrocarbon include polyethylene wax, polypropylene wax, Fischer-Tropsch wax, acid amide compounds, and acid imide compounds.

Examples of the modified wax include amine-modified polypropylene, acrylic acid-modified, fluorine-modified, olefin-modified wax, urethane type wax, alcohol type wax, and the like.
Examples of the hydrogenated wax include hydrogenated castor oil, castor oil derivatives, stearic acid, lauric acid, myristic acid, palmitic acid, sebacic acid, undecylenic acid, heptyl acid, maleic acid, highly maleated oil, blowing oil, cyclopentadiene oil And synthetic waxes.

Examples of the natural wax include animal waxes, mineral waxes, and petroleum waxes. Examples of the animal waxes include lanolin, spermaceti, stew wax (whale oil), and wool wax.
Examples of the mineral wax include montan wax, montan ester wax, ozokerite, ceresin, and fatty acid ester.
Examples of the petroleum wax include paraffin wax, microcrystalline wax, and petrolatum.

The melting point of the release agent can be appropriately selected according to the purpose, but is preferably 50 to 160 ° C, more preferably 60 to 120 ° C, and particularly preferably 70 to 100 ° C.
If the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, fixing failure may occur, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  The content (total content) of the release agent in the toner is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass. When the content is less than 0.1% by mass, the releasability is insufficient, and the hot offset property during fixing and the wrapping property with respect to the fixing member may be deteriorated. The fluidity / transferability of the toner and the durability of the developer may be poor.

In the toner of the present invention, a wax dispersant is preferably added in order to improve dispersibility when the waxes are finely dispersed by wet pulverization. The wax dispersant is not particularly limited and may be appropriately selected depending on the purpose. Basically, a material having a portion having a high affinity for wax and a portion having a high affinity for binder resin is used. . For example, a polyethylene wax grafted with a styrene- (meth) acrylic acid ester copolymer is preferably used.
The content of the wax dispersant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the content is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the total amount of added wax.

  The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include colorants, resin fine particles, non-reactive polyester resins, charge control agents, inorganic fine particles, fluidity improvers, and cleaning agents. Property improvers, magnetic materials, metal soaps, and the like.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine 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, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Degreen Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Lithbon, etc.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.
When the content is less than 1% by mass, a desired coloring degree may not be obtained, and when it exceeds 15% by mass, an unnecessarily high coloring degree may be obtained.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, 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, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

The resin fine particles are generally added for the purpose of controlling the toner shape (average circularity, particle size distribution, etc.). The resin fine particles adhere to or bind to the surface of the toner when the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen-containing compound are dispersed in the aqueous medium to form toner particles. Etc.
The resin fine particle is not particularly limited as long as it is a resin capable of forming an aqueous dispersion in the aqueous medium, can be appropriately selected from known resins, and may be a thermoplastic resin, It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, And polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a mixture thereof are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, and specific examples include styrene- (meth) acrylic ester resin, styrene-butadiene copolymer, (meth) acrylic acid- Examples include acrylic ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

  The glass transition temperature (Tg) of the resin fine particles is preferably 40 to 100 ° C. The weight average molecular weight of the resin fine particles is preferably 9,000 to 200,000. When the Tg is less than 40 ° C. and / or the weight average molecular weight is less than 9,000 in the resin fine particles, the storage stability of the toner deteriorates, and blocking may occur during storage and in the developing machine. When the Tg exceeds 100 ° C. and / or the weight average molecular weight exceeds 200,000, the resin fine particles may inhibit the adhesion to the fixing paper, and the minimum fixing temperature may increase.

The content of the resin fine particles in the toner is preferably 0.5 to 5.0% by mass, and more preferably 1.0 to 4.0% by mass.
When the content is less than 0.5% by mass, the storability of the toner deteriorates, and blocking may occur during storage and in the developing machine. When the content exceeds 5.0% by mass, The resin fine particles inhibit the exudation of the wax, and the wax releasability effect cannot be obtained, and offset may occur.

When the non-reactive polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the non-reactive polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The non-reactive polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.
The weight average molecular weight of the non-reactive polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and 2,000 as measured by GPC (gel permeation chromatography). ˜8,000 is particularly preferred. When the weight average molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
As a hydroxyl value of the said non-reactive polyester resin, 5 or more are preferable, 10-120 are more preferable, and 20-80 are still more preferable. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
As an acid value of the said non-reactive polyester resin, 1-30 are preferable and 5-20 are more preferable. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

When the non-reactive polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the non-reactive polyester resin (PE) is 5 / 95-80 / 20 are preferable, 5 / 95-30 / 70 are more preferable, 5 / 95-25 / 75 are still more preferable, and 7 / 93-20 / 80 are especially preferable.
When the mixing mass ratio of the non-reactive polyester resin (PE) exceeds 95, the hot offset resistance may deteriorate, and when it is less than 20, the low-temperature fixability may deteriorate.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. 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 the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner directly when dissolved or dispersed in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the adhesive base material, the presence or absence of additives, the dispersion method, and the like, and cannot be defined generally. 0.1-10 mass parts is preferable with respect to part, and 0.2-5 mass parts is more preferable. If the content is less than 0.1 parts by mass, background stains, toner scattering, etc. may occur. If the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. The electrostatic attraction force with the developing roller is increased, and the fluidity of the developer and the image density may be reduced.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, for example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, etc. Is mentioned.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

  The shape and size of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose. The following pigment dispersibility, transparency, image density, average circularity, It is preferable to have a mass average particle diameter or the like.

The pigment dispersibility represents the dispersion state of the insoluble pigment in the toner. For example, the chroma (C *) measured using a spectrometer (X-Light, 938 Spectrodensitometer) is 72. The above is preferable, 76 or more is more preferable, and 78 or more is particularly preferable.
When the pigment dispersibility is less than 72, the effect of using the soluble pigment precursor is not sufficient, the dispersibility of the colorant is not sufficient, the color reproduction range is narrow, and the transparency and coloring are improved. Is low, and a high image quality comparable to a full-color image formed by silver salt photography or printing may not be obtained. On the other hand, if it is 72 or more, the dispersibility of the insoluble pigment as a colorant is good. It is advantageous in that the toner has a wide color reproduction range, can sufficiently improve transparency and color clarity, and can obtain a high image quality comparable to a full-color image formed by a silver salt photography method or a printing method. is there.

The transparency is also called “cloudiness”, and the haze value is preferably less than 20%, more preferably less than 10%.
If the haze is 20% or more, the transparency is not sufficient, the color reproduction range is narrow, the effect of improving transparency and clarity is low, and a full-color image formed by a silver salt photography method or a printing method is used. Comparable high image quality may not be obtained. On the other hand, if it is less than 20, the dispersibility of the insoluble pigment as a colorant is good, the color reproduction range is wide, and transparency and color are sufficiently improved. This is advantageous in that the toner can provide a high image quality comparable to a full-color image formed by a silver salt photography method or a printing method.
The haze degree is measured using, for example, a direct reading haze computer HGM-2DP type (manufactured by Suga Test Instruments Co., Ltd.) with respect to a toner image (solid image) formed on a transparent sheet (eg, OHP sheet). Can do.

The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is determined by using, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.) and copying paper (TYPE).
6000 <70W> (manufactured by Ricoh Co., Ltd.), a solid image having a developer adhesion amount of 1.00 ± 0.05 mg / cm ² was formed at a fixing roller surface temperature of 160 ± 2 ° C., and the resulting solid image It is possible to measure the image density at arbitrary six locations in the above by measuring using a spectrometer (X-Light, 938 Spectrodensitometer) and calculating the average value.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles, and is preferably 0.940 to 0.995, for example, 0.945 to 0 .955 is more preferred. The particles having an average circularity of less than 0.94 are preferably 10% or less.
If the average circularity is less than 0.940, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.995, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and transfer belt, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. As a result, the accumulated toner may become a transfer residual toner on the photoconductor, which may cause background smearing of the image, or may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).

The mass average particle diameter of the toner is preferably 4 to 8 μm.
When the mass average particle size is less than 4 μm, in the two-component developer, the toner may be 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 reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image having an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio of the mass average particle diameter to the number average particle diameter (mass average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.
When the ratio of the mass average particle diameter to the number average particle diameter (mass average particle diameter / number average particle diameter) exceeds 1.25, the two-component developer may cause the surface of the carrier to be agitated over a long period of time in the developing device. The toner may be fused to reduce the charging ability of the carrier. With a one-component developer, the toner filming on the developing roller or the toner is thinned, causing the toner to be fused to a member such as a blade. In addition, it may be 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 size may increase.

  The mass average particle diameter and the ratio of the mass average particle diameter to the number average particle diameter (mass average particle diameter / number average particle diameter) are, for example, a particle size measuring instrument ““ Coulter Counter TAII ”manufactured by Coulter Electronics Co., Ltd. Can be measured.

  In the toner of the present invention, the insoluble pigment exists in the state of the soluble pigment precursor before the production of the toner, and is uniformly dissolved or dispersed in a solvent containing the solid content material of the toner. Therefore, the insoluble pigment is highly dispersed in the toner of the present invention obtained by converting the soluble pigment precursor into the insoluble pigment. For this reason, the toner of the present invention has a wide color reproduction range and can sufficiently improve transparency and clarity. When an image is formed using the toner of the present invention, the toner is formed by a silver salt photography method or a printing method. High image quality comparable to full-color images can be obtained. In addition, the toner of the present invention includes the adhesive base formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. Excellent properties such as properties, fluidity, transferability, and fixability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.

  The toner of the present invention can be produced by a known method, but can be suitably produced by the toner production method of the present invention described later.

(Toner production method)
The toner production method of the present invention includes at least an adhesive base material production step and a wet pulverization step, and further includes other steps appropriately selected as necessary.

-Adhesive substrate production process-
In the adhesive base material generation step, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are dispersed in the aqueous medium and reacted to form an adhesive base material while producing a toner. It is a process to obtain.
In the adhesive substrate generation step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, Synthesis of active hydrogen group-containing compounds).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared in the organic solvent by containing the active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, the pigment, the release agent, the charge control agent, and the non-reacting agent. It can be carried out by dissolving or dispersing a toner raw material such as a reactive polyester resin.
It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are 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 raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.

The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be produced by extending or cross-linking both in the phase, or (3) the organic solvent phase is added and mixed in the aqueous medium and then the active hydrogen group-containing The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  As the reaction conditions for generating the adhesive substrate by subjecting the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound to an extension reaction or a crosslinking reaction by the emulsification / dispersion, There is no limitation, and it can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, preferably 2 Time to 24 hours are more preferable, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent (for example, the isocyanate group-containing polyester prepolymer (A)), the pigment, the release agent, Examples thereof include a method in which the toner raw material such as the charge control agent and the non-reactive polyester resin is added and dispersed by a shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples include a 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 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 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the emulsification / dispersion, the usage amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner raw material.
When the amount used is less than 50 parts by mass, the toner raw material is poorly dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost is high. May be.

In the emulsification / dispersion, it is preferable to use a dispersant from the viewpoint of sharpening the particle size distribution and performing stable dispersion as necessary.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. 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- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

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 acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids 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-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

-Wet grinding process-
The wet pulverization step is a step of preparing a wax dispersion by wet pulverization of synthetic ester wax and plant wax.
The wet pulverization method is not particularly limited, and can be appropriately selected using a known pulverizer or the like. Examples of the pulverizer include a bead mill (“Ultra Visco Mill”; 8 mm glass beads) are suitable.
The viscosity of the wax dispersion at 25 ° C. is preferably 1500 cp or less, and more preferably 100 to 1200 cp. If the viscosity exceeds 1500 cp, wet pulverization may be difficult.

In this way, the obtained toner particles are mixed with particles such as the release agent and the charge control agent, or further applied with a mechanical impact force so that the particles such as the release agent are separated from the surface of the toner particles. Can be prevented from desorbing.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

Here, a preferred specific example of the toner production method of the present invention is shown below.
-Adhesive substrate production process-
-Preparation of aqueous medium phase (aqueous phase)-
In a reaction vessel equipped with a stirrer and a thermometer, water, sodium salt of ethylene oxide methacrylate adduct sulfate, styrene, methacrylic acid, butyl acrylate, butyl thioglycolate, and ammonium persulfate were charged at 400 rpm. Stir for 15 minutes to give a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, a 1% by mass ammonium persulfate aqueous solution was added to the reaction solution, and aged for 5 hours at 75 ° C. An aqueous dispersion (hereinafter referred to as “fine particle dispersion 1”) is prepared.
Thereafter, water, the “fine particle dispersion 1”, a 48.5 mass% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and ethyl acetate are mixed and stirred to prepare a milky white liquid (hereinafter referred to as “water phase”). .

--Synthesis of low molecular weight polyester--
A reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube is charged with bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 3-mole adduct, terephthalic acid, adipic acid, and dibutyltin oxide under normal pressure. , Reacted at 230 ° C. for 8 hours. Next, the reaction solution is reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then trimellitic anhydride is added to the reaction vessel, and the reaction is performed at 180 ° C. for 2 hours under normal pressure. Synthesize.

--Synthesis of prepolymer--
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, trimellitic anhydride, and dibutyltin oxide are charged. The reaction was carried out at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
Then, the “intermediate polyester 1”, isophorone diisocyanate, and ethyl acetate were charged into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours to prepare prepolymer 1 ( A polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
Isophoronediamine and methyl ethyl ketone were charged into a reaction vessel equipped with a stirring bar and a thermometer, and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).

-Preparation of masterbatch (MB)-
Water, copper phthalocyanine pigment as the colorant, and polyester resin were added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Preparation of organic solvent phase-
(Wet grinding process)
In a reaction vessel equipped with a stir bar and a thermometer, the "low molecular weight polyester 1" carnauba wax, pentaerythritol tetrabehenate, wax dispersant (polyethylene wax grafted with styrene-butyl acrylate copolymer) ) And ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, the master batch and ethyl acetate were charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
The obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation, 0.8 mm glass beads), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0 The above pigment and carnauba wax were dispersed in 9 passes under the condition of filling 80% by volume of 5 mm zirconia beads.
Next, a 65 mass% ethyl acetate solution of the low molecular weight polyester was added to the obtained dispersion liquid after 9 passes. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.

--Emulsification / Dispersion--
Into a reaction vessel, the organic solvent phase, the prepolymer, and the ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). The aqueous phase was added, and the mixture was mixed for 20 minutes at a rotational speed of 13,000 rpm using a TK homomixer, and emulsified and dispersed to prepare an emulsified slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the emulsified slurry was aged at 45 ° C. for 4 hours.

--- Washing and drying--
The emulsified slurry after aging was filtered under reduced pressure, ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 5,000 rpm for 10 minutes), and then filtered. 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, and it mixed by TK type | mold homomixer (30 minutes at the rotation speed of 5,000 rpm), Then, it filtered under reduced pressure. 10 mass% hydrochloric acid was added to the filter cake obtained here, and after mixing with a TK homomixer (rotation speed: 5,000 rpm for 10 minutes), the mixture was filtered. Ion-exchanged water was added to the filter cake obtained here and mixed with a TK homomixer (rotation speed: 5,000 rpm for 10 minutes) and then filtered twice to obtain “final filter cake 1”. It was.
The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier, pulverized with a mixer, and sieved with a mesh of 44 μm to obtain a toner.
Then, the toner of the present invention can be produced by mixing hydrophobic silica and hydrophobic titanium oxide with the obtained toner using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.).

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is made thin. Therefore, toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 150 μm, and more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion 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, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner of the present invention, it is possible to achieve a balance between chargeability and fixability during image formation, and stably form high-quality images. .
The developer of the present invention can be suitably 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. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral irregularity is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(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. A developing means for forming the image forming apparatus, and further having other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. .
The developing means includes a developer container that contains the toner or developer of the present invention, and an electrostatic latent image 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 of the present invention can be detachably mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

Here, as the process cartridge, for example, as shown in FIG. 1, a photosensitive member 101 is incorporated, and in addition, a charging unit 102, an exposure unit 103, a developing unit 104, a transfer unit 105, a cleaning unit 107, and a charge eliminating unit 108. In addition, other members are included as necessary.
The photoreceptor 101 includes a support and a photosensitive layer including a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order on the support. As the charging member 102, a known charging member is used as described above, and an electric field is applied to the photoreceptor.
A light source capable of writing with high resolution is used for the exposure means 103. An arbitrary charging member (preferably scorotron charging) is used for the charging means 102.

  The image forming apparatus of the present invention is configured by integrally combining the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge, and this unit is configured to be detachable from the apparatus main body. Also good. Alternatively, at least one of a charging device, an image exposure device, a developing device, a transfer device, a separator, and a cleaning device is integrally supported together with a photosensitive member to form a process cartridge, which is a single unit that is detachable from the apparatus main body. Further, it may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
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 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 further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon and the like are 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 utilizing 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 surface side of the electrostatic latent image carrier may be adopted.

-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 means is not particularly limited as long as it can be developed using, for example, the toner or 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 developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  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 latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, 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, 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 usually 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 electrophotographic 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 electrophotographic color toner removed in 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 means is a process for controlling the respective steps, and can be suitably performed by the control means.
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.

  The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

Here, an aspect of the image forming apparatus of the present invention will be described with reference to FIG.
FIG. 2 is a schematic diagram for explaining the image forming apparatus of the present invention, and a modified example as described later also belongs to the category of the present invention.
A photosensitive member 201 as an electrostatic latent image carrier has a photosensitive layer including at least a photosensitive layer or a charge generation layer and a charge transport layer in this order on a support. The layer contains an azo compound represented by the structural formula (1) as a charge generating substance. Although the photoconductor 201 has a drum shape, it may have a sheet shape or an endless belt shape.
As the charging member 203, a wire-type charging member or a roller-shaped charging member is used. A scorotron charging member is preferably used for high-speed charging. Although the photosensitive member is charged by this charging member, the higher the electric field strength applied to the photosensitive member, the better the dot reproducibility.
The image exposure unit 205 uses a light source that can ensure high luminance and can write at high resolution (600 dpi or higher resolution) such as a light emitting diode (LED), a semiconductor laser (LD), and electroluminescence (EL). .

  A known charger can be used as the transfer means, but a combination of the transfer charger 210 and the separation charger 211 as shown in FIG. 2 is effective. In addition, a transfer belt and a transfer roller can be used, and it is desirable to use a contact type such as a transfer belt or a transfer roller that generates less ozone. As a voltage / current application method at the time of transfer, either a constant voltage method or a constant current method can be used, but the transfer charge amount can be kept constant, and a constant voltage with excellent stability can be used. The current method is more desirable.

The developing member 206 has one developing sleeve, and the toner developed on the photoreceptor 1 is transferred to the transfer paper 209.
Further, the toner image formed on the photosensitive member is transferred to the transfer paper and becomes an image on the transfer paper. At this time, there are two methods. One is a method of directly transferring the toner image developed on the surface of the photoreceptor as shown in FIG. 2 to the transfer paper, and the other is once the toner image is transferred from the photoreceptor to the intermediate transfer body, and this is transferred to the transfer paper. It is the method of transferring to. Either case can be used in the present invention.
As such a transfer member, a known member can be used as long as the structure of the present invention can be satisfied.
When positive (negative) charging is performed on the photosensitive member and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.

  As a light source such as the static elimination lamp 2, general light emitting materials such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser (LD), and an electroluminescence (EL) can be used. . Various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.

Such a light source or the like irradiates the photosensitive member with light by providing a process such as a transfer process, a static elimination process, a cleaning process, or a pre-exposure using light irradiation in addition to the process shown in FIG.
This neutralization mechanism can be omitted when the AC component is superposed and used in the previous charging method, or when the residual potential of the photoreceptor is small. Further, instead of optical static elimination, an electrostatic static elimination mechanism (for example, a static elimination brush applied with a reverse bias or grounded) can be used. In FIG. 2, 208 is a registration roller, and 212 is a separation claw.

  In addition, the toner developed on the photoconductor 201 by the developing unit 206 is transferred to the transfer paper 209. When toner remaining on the photoconductor 201 is generated, the fur brush 214 and the blade 215 remove the toner from the photoconductor. Removed. Cleaning may be performed only with a cleaning brush, and a known brush such as a fur brush or a mag fur brush is used as the cleaning brush.

  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. The image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 illustrated in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another 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. The image forming apparatus 100 illustrated in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 illustrated in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except that the cyan developing unit 45C is directly opposed, it has the same configuration as the image forming apparatus 100 shown in FIG. 3 and exhibits the same function and effect. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

Another 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. The tandem image forming apparatus shown in FIG. 5 is a tandem color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 5. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus 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 contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each of the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 6), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is an intermediate transfer member. The image forming apparatus includes a transfer charger 62 for transferring the image onto 0, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) 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. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

Further, in the fixing step of the image forming apparatus of the present invention, the fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. And a fixing device that heats and fixes a recording material on which an unfixed image is formed between the film and the pressure member may be used.
The fixing device can efficiently shorten the rise time.

Here, the fixing device shown in FIG. 7 includes a heating roller 1 heated by electromagnetic induction of the induction heating unit 6, a fixing roller 2 arranged in parallel to the heating roller 1, and the heating roller 1 and the fixing roller 2. An endless belt-like heat-resistant belt (toner heating medium) 3 that is stretched and heated by the heating roller 1 and rotated in the direction of arrow A by at least one of these rollers, and a fixing roller via the belt 3 2 and a pressure roller 4 that rotates in the forward direction with respect to the belt 3.
The heating roller 1 is made of, for example, a hollow cylindrical magnetic metal member such as iron, cobalt, nickel, or an alloy of these metals, and has an outer diameter of 30 mm and a thickness of 1 mm, for example, and has a low heat capacity and a high temperature rise. It has become.
The fixing roller 2 includes, for example, a metal core 2a made of stainless steel or the like and an elastic member 2b in which a heat resistant silicone rubber is solid or foamed and covered with the core 2a. In order to form a contact portion having a predetermined width between the pressure roller 4 and the fixing roller 2 by the pressing force from the pressure roller 4, the outer diameter is set to about 40 mm and larger than the heating roller 1. The elastic member 2b has a thickness of about 0.5 to 30 mm and a hardness of about 20 to 80 ° (JIS 6301 hardness). With this configuration, the heat capacity of the heating roller 1 is smaller than the heat capacity of the fixing roller 2, so that the heating roller 1 is rapidly heated and the warm-up time is shortened.
The belt 3 stretched between the heating roller 1 and the fixing roller 2 is heated at the contact portion W1 with the heating roller 1 heated by the induction heating means 6. The inner surface of the belt 3 is continuously heated by the rotation of the rollers 1 and 2, and as a result, the entire belt is heated.

The thickness of the release layer 3 is preferably about 5 to 50 μm, particularly about 20 μm. By doing so, the toner image T formed on the recording material 13 is sufficiently wrapped by the surface layer portion of the belt 3, so that the toner image T can be uniformly heated and melted.
When the thickness of the release layer 3 is smaller than 5 μm, the heat capacity of the belt 3 becomes small and the belt surface temperature rapidly decreases in the toner fixing step, so that the fixing performance cannot be sufficiently ensured. Further, when the thickness of the release layer 3 is larger than 50 μm, the heat capacity of the belt 3 is increased and the time required for warm-up is increased. In addition, in the toner fixing process, the belt surface temperature is difficult to decrease, the agglomeration effect of the melted toner at the fixing portion outlet cannot be obtained, the belt releasability is reduced, and the toner adheres to the belt. Hot offset occurs.
As a base material for the belt 3, a heat-resistant resin layer such as a fluorine resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a PEEK resin, a PES resin, or a PPS resin is used instead of the heat generating layer 3a made of the metal. May be used.

The pressure roller 4 includes, for example, a metal core 4a made of a metal cylindrical member having a high thermal conductivity such as copper or aluminum, and an elastic material having high heat resistance and toner releasability provided on the surface of the metal core 4a. It is comprised from the member 4b. In addition to the above metal, SUS may be used for the core metal 4a.
The pressure roller 4 presses the fixing roller 2 via the belt 3 to form the fixing nip portion N, but in this embodiment, the pressure roller 4 is harder than the fixing roller 2. As a result, the pressure roller 4 bites into the fixing roller 2 (and the belt 3), and this bite follows the circumferential shape of the recording material 13 and the pressure roller 4 surface. Has the effect of facilitating. The outer diameter of the pressure roller 4 is about 40 mm, which is the same as that of the fixing roller 2, but the wall thickness is about 0.3 to 20 mm, which is thinner than the fixing roller 2, and the hardness is about 10 to 70 ° (JIS 6301 hardness). As described above, it is harder than the fixing roller 2.

As shown in FIGS. 7 and 8A and B, an induction heating means 6 for heating the heating roller 1 by electromagnetic induction includes an excitation coil 7 as a magnetic field generation means and a coil guide plate 8 around which the excitation coil 7 is wound. And have. The coil guide plate 8 has a semi-cylindrical shape arranged close to the outer peripheral surface of the heating roller 1. As shown in FIG. 8B, the excitation coil 7 includes a long excitation coil wire along the coil guide plate 8. Thus, the heating roller 1 is wound alternately in the axial direction.
The exciting coil 7 is connected to a driving power source (not shown) whose oscillation circuit has a variable frequency.
Outside the excitation coil 7, a semi-cylindrical excitation coil core 9 made of a ferromagnetic material such as ferrite is fixed to the excitation coil core support member 12 and is disposed close to the excitation coil 7. In the present embodiment, the exciting coil core 9 has a relative permeability of 2500.

A high frequency alternating current of 10 kHz to 1 MHz, preferably a high frequency alternating current of 20 kHz to 800 kHz is supplied to the exciting coil 7 from a driving power source, thereby generating an alternating magnetic field. The alternating magnetic field acts on the heating roller 1 and the heat generating layer 3a of the belt 3 in the contact area W1 between the heating roller 1 and the heat-resistant belt 3 and in the vicinity thereof, and the direction B prevents the change of the alternating magnetic field inside these. Eddy current I flows through
This eddy current I generates Joule heat according to the resistance of the heating roller 1 and the heat generating layer 3a, and the belt 3 having the heating roller 1 and the heat generating layer 3a mainly in the contact area between the heating roller 1 and the belt 3 and in the vicinity thereof. Is heated by electromagnetic induction.
The belt 3 heated in this way is detected by temperature detecting means 5 comprising a thermosensitive element such as a thermistor arranged in contact with the inner surface side of the belt 3 in the vicinity of the inlet side of the fixing nip N. The belt inner surface temperature is detected.

  In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention is used, it is excellent in various properties such as hot offset property at the time of fixing, wrapping property to a fixing member, productivity is improved, and low temperature fixing is performed. And color reproducibility can be achieved, and a clear high-quality image can be obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Comparative Example 1)
-Adhesive substrate production process-
-Preparation of aqueous medium phase (aqueous phase)-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of an ethylene oxide adduct sulfate (“Eleminol RS-30”; manufactured by Sanyo Chemical Industries Ltd.), 80 styrene 1 part by weight, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, 12 parts by weight of butyl thioglycolate, and 1 part by weight of ammonium persulfate were stirred for 15 minutes at 400 rpm, and the white emulsion was Obtained. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added to the reaction solution, and aged for 5 hours at 75 ° C., and a vinyl resin (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt co-polymerized. An aqueous dispersion (hereinafter referred to as “fine particle dispersion 1”) was prepared.
The obtained “fine particle dispersion 1” had a volume average particle size of 120 nm as measured with a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Shimadzu Corporation). Further, a part of the obtained “fine particle dispersion 1” was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the weight average molecular weight (Mw) was 30,000.
Then, 990 parts by mass of water, 83 parts by mass of the above-mentioned “fine particle dispersion 1”, 37 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate was mixed and stirred to prepare a milky white liquid (hereinafter referred to as “aqueous phase”).

--Synthesis of low molecular weight polyester--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propylene oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 adipic acid 46 Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after the reaction solution was reacted for 5 hours under reduced pressure of 10 to 15 mmHg, 45 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Molecular polyester was synthesized.
The obtained low molecular weight polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,500, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Then, 410 parts by mass of the “intermediate polyester 1”, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. By reacting for a time, prepolymer 1 (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen group-containing compound) was 418.

-Preparation of masterbatch (MB)-
1200 parts by weight of water, 1200 parts by weight of copper phthalocyanine pigment (Toyo Ink Manufacturing Co., Ltd., LIONOL BLUE 7351) as a colorant, and 1200 parts by weight of a polyester resin (“RS801”; manufactured by Sanyo Chemical Industries, Ltd.) It mixed with the Henschel mixer (made by Mitsui Mining Co., Ltd.). The mixture was kneaded with a two-roller at 100 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Preparation of organic solvent phase-
(Wet grinding process)
300 parts by weight of the above-mentioned “low molecular polyester 1”, 100 parts by weight of carnauba wax, wax dispersant (polyethylene wax grafted with styrene-butyl acrylate copolymer) in a reaction vessel equipped with a stir bar and a thermometer ) 20 parts by mass and 780 parts by mass of ethyl acetate were charged, the temperature was raised to 80 ° C. with stirring, the temperature was maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), three passes were performed under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 80% by volume of 0.8 mm glass beads were filled. Carnauba wax was wet pulverized. Further, 6 passes (9 passes in total) were subjected to wet grinding. For the wax dispersion after 3 passes and the wax dispersion after 9 passes, the particle size distribution and viscosity were measured as follows. The results are shown in Table 1.
<Measurement of particle size distribution>
The obtained dispersion was measured using a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Shimadzu Corporation).
<Measurement of viscosity>
The obtained dispersion was measured with a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at 60 rpm and 25 ° C.

  Next, 600 parts by mass of the wax dispersion obtained after 9 passes, 120 parts by mass of the master batch, 1213 parts by mass of a 50% by mass ethyl acetate solution of the low molecular weight polyester, and 30 parts by mass of ethyl acetate were charged in the reaction vessel. The raw material solution was obtained by stirring and mixing for 1 hour. The solid content concentration of the obtained organic solvent phase was 50.0% by mass.

--Emulsification / Dispersion--
In 1963 parts by mass of the organic solvent phase in the reaction vessel, 267 parts by mass of the prepolymer and 2.9 parts by mass of the ketimine compound are charged, and 3 times at 5,000 rpm using a TK type homomixer (manufactured by Tokushu Kika). After mixing for 3 minutes, 3350 parts by mass of the aqueous phase was added to the reaction vessel, and the mixture was mixed for 20 minutes at 13,000 rpm using a TK homomixer, and emulsified and dispersed to prepare an emulsified slurry. did.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the emulsified slurry was aged at 45 ° C. for 4 hours.
The obtained emulsified slurry had a volume average particle size of 5.7 μm and a number average particle size of 5.4 μm as measured with Multisizer II (manufactured by Coulter Counter).

--- Washing and drying--
After 100 parts by mass of the emulsified slurry after aging was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 5,000 rpm), and then filtered. . 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, and it mixed by TK type homomixer (30 minutes at the rotation speed of 5,000 rpm), Then, it filtered under reduced pressure. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, and it mixed with TK type homomixer (10 minutes at the rotation speed of 5,000 rpm), and then filtered. An operation of adding 300 parts by mass of ion-exchanged water to the obtained filter cake, mixing with a TK homomixer (10 minutes at a rotation speed of 5,000 rpm), and then filtering was performed twice. "
The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier, pulverized with an opening mixer, and then sieved with a mesh of 44 μm to obtain a toner.
Then, with respect to 100 parts by mass of the obtained toner, 1.0 part by mass of hydrophobic silica and 0.5 part by mass of hydrophobic titanium oxide were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), so that Comparative Example 1 Toner was produced.

(Comparative Example 2)
In Comparative Example 1, except that 100 parts by weight of carnauba wax was changed to 100 parts by weight of pentaerythritol tetrabenate (weight average molecular weight (Mw) = about 1300) in the step of preparing the organic solvent phase, Similarly, the toner of Comparative Example 2 was produced.
In the same manner as in Comparative Example 1, the particle size distribution and viscosity of the wax dispersion were measured. The results are shown in Table 1.

Example 1
In Comparative Example 1, 100 parts by weight of carnauba wax was changed to 50 parts by weight of carnauba wax and 50 parts by weight of pentaerythritol tetrabehenate (weight average molecular weight (Mw) = about 1300) in the organic solvent phase preparation step. A toner of Example 1 was produced in the same manner as in Comparative Example 1 except that.
In the same manner as in Comparative Example 1, the particle size distribution and viscosity of the wax dispersion were measured. The results are shown in Table 1.

(Example 2)
In Comparative Example 1, 100 parts by weight of carnauba wax was changed to 70 parts by weight of carnauba wax and 30 parts by weight of pentaerythritol tetrabehenate (weight average molecular weight (Mw) = about 1300) in the organic solvent phase preparation step. A toner of Example 2 was produced in the same manner as in Comparative Example 1 except that.
In the same manner as in Comparative Example 1, the particle size distribution and viscosity of the wax dispersion were measured. The results are shown in Table 1.

表１の結果から、比較例２のペンタエリスリトールテトラべへネートは、実施例１、２及び比較例１のワックスに比べて微分散し難く、特に２μｍ以上の粗大な粒子が残りやすく、分散液の粘度が高いため、生産性が低下するが、実施例１のようにペンタエリスリトールテトラべへネートとカルナウバワックスとを併用することにより、改善されることが認められる。

From the results in Table 1, the pentaerythritol tetrabehenate of Comparative Example 2 is less likely to finely disperse than the waxes of Examples 1 and 2 and Comparative Example 1, and in particular, coarse particles of 2 μm or more tend to remain, and the dispersion liquid. Although the productivity is lowered due to the high viscosity, it can be seen that the improvement can be achieved by using pentaerythritol tetrabehenate and carnauba wax together as in Example 1.

  About each obtained toner, the volume average particle diameter and the particle size distribution, the fixing property, and the toner physical property of the winding property to the belt were measured as follows. The results are shown in Table 2.

<Toner particle size>
The mass average particle diameter and number average particle diameter (Dn) of each toner were measured with a particle size measuring device (“Coulter Counter TAII”; manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. From these results, (mass average particle diameter / number average particle diameter (Dn)) was calculated.

<Fixability evaluation>
Using an oilless remodeling machine of a digital full-color printer (Ricoh Co., Ltd., IPSiO CX8200), a toner adhesion amount of 0. Adjustment was made so that a solid image of 85 mg / cm ² was obtained, and the temperature of the fixing belt was adjusted to be variable. Using the image forming apparatus in this state, the fixed image was visually determined, and the lowest temperature (hot offset temperature) at which the offset occurred was measured. Further, the lowest temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a sand eraser was 70% or more was determined as the minimum fixing temperature. The results are shown in Table 1. A hot offset temperature lower than about 190 ° C. was judged as defective.

<Evaluation of winding property to belt>
In the fixability evaluation, when the paper fixed from the fixing nip portion comes out, it is judged visually whether the paper fixed on the fixing member (fixing belt) is wound or not, and the lowest temperature at which the winding occurs is determined. (Temperature generation temperature) was measured. In addition, the thing whose winding generation temperature is lower than about 190 degreeC was judged to be unsatisfactory.

  The toner of the present invention is used in a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. The present invention can be applied to a developer containing the toner, an image forming method using the developer, an image forming method loaded with the developer, and a process cartridge holding the developer. Further, a toner used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine, etc. using a direct or indirect electrophotographic multicolor image developing system, a developer containing the toner, and an image formation using the developer It can be used for a method, an image forming method loaded with the developer, and a process cartridge holding the developer.

FIG. 1 is a schematic explanatory diagram showing an example of the process cartridge of the present invention. FIG. 2 is a schematic explanatory diagram illustrating an example of the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory diagram showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory diagram showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory diagram showing an example in which the image forming method of the present invention is carried out by the image forming apparatus (tandem color image forming apparatus) of the present invention. 6 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. FIG. 7 is an explanatory diagram showing a fixing device according to an embodiment of the present invention. FIG. 8A is a sectional view showing the arrangement of the excitation coils of the induction heating means in the fixing device of the present invention, and FIG. 8B is a side view showing the arrangement of the excitation coils of the induction heating means in the fixing device of the present invention.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 71 Cleaning blade 72 Support member 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming apparatus 101 Photoconductor 102 Charging means 103 Exposure 104 Developing means 105 Transfer body 106 Transfer means 107 Cleaning means 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copying device main body 200 Feeding table 201 Photosensitive body 202 Static elimination lamp 203 Charger charger 204 Eraser 205 Image exposure unit 206 Developing unit 207 Pre-transfer charger 208 Registration roller 209 Transfer paper 210 Transfer charger 211 Separation charger 212 Separation claw 213 Charger before cleaning 214 Fur brush 215 Cleaning brush 300 Scanner 400 Automatic document feeder (ADF)

Claims (6)

An organic solvent phase in which an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound and a wax dispersion are dissolved or dispersed are dispersed and reacted in an aqueous medium to form an adhesive substrate. An adhesive base material production step for obtaining toner, and at least a wet grinding step of preparing a wax dispersion by wet grinding a synthetic ester wax and a vegetable wax, wherein the solvent of the wax dispersion is ethyl acetate The synthetic ester wax is a wax synthesized from any of pentaerythritol tetramyristate, pentaerythritol tetrapalmitate, pentaerythritol tetrastearate, and pentaerythritol tetrabehenate, and the plant ester wax is Tona, which is carnauba wax The method of production. Method for producing a toner according to claim 1 synthesis ester wax is a branched type. The method for producing a toner according to claim 1, wherein a mixing mass ratio of the synthetic ester wax and the plant wax (synthetic ester wax: plant wax) is 1: 0.1-10. The method for producing a toner according to claim 1, wherein the adhesive substrate contains a polyester resin. The method for producing a toner according to claim 4, wherein the polyester resin contains a urea-modified polyester resin. The method for producing a toner according to claim 1, wherein the viscosity of the wax dispersion at 25 ° C. is 1500 cp or less.

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