JP4925776B2 - Image forming method, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to an electrophotographic image forming method, a process cartridge, and an image forming apparatus. The present invention further relates to an image forming method, a process cartridge, and an image forming apparatus using an electrostatic charge developing toner composition used in a copying machine, a printer, or the like applying electrophotographic technology.

Conventionally, as a method for collecting the residual toner on the electrostatic latent image bearing member after transfer, a method of using a cleaning member and collecting it in a container for storing waste toner has been widely adopted. In a contact cleaning system represented as a cleaning system, a system is adopted in which an elastic body is brought into contact with an electrostatic latent image carrier and waste toner is collected in a container.
The method of collecting the residual toner on the electrostatic latent image carrier after transfer using these cleaning members is a method that is not suitable for environmental measures required in this field from the viewpoint of generating waste toner, It is necessary to secure a space for the container, which is not suitable for downsizing and space saving.
One of the techniques for dealing with this environmental problem is a cleanerless image forming method. This is an image forming method in which image recording is performed without using an apparatus for cleaning residual toner after transfer. By using this cleanerless image forming method, it becomes possible to exclude the cleaning device, and the toner remaining on the electrostatic latent image carrier can be used again at the time of image formation, thereby reducing the environmental load. This is an extremely useful technique as an image forming device that can be used.
Further, these cleanerless image forming methods have an aspect that the apparatus can be miniaturized because no storage container is used. That is, it is possible to satisfy the need for downsizing of the apparatus, which is one of the demands for printers and copying machines using the electrophotographic system. Therefore, the cleanerless image forming method is a very effective technique that can cope with environmental loads and contribute to downsizing of the image forming apparatus.
The cleanerless image forming method is known from, for example, Patent Documents 1 to 4 and the like.
However, in the method described in Patent Document 1 or 2, the charge of the residual toner after transfer is remarkably lowered, and is uncharged or reversely charged. Therefore, when toner adheres to the brush charger, it becomes difficult to remove. . In Patent Document 3 or 4, since the remaining toner is charged to a polarity opposite to the original toner polarity, it is difficult to make the charging polarity completely uniform.

After the developed toner is transferred from the latent electrostatic image bearing member, the toner remaining on the surface of the latent electrostatic image bearing member is remarkably lowered in charge and is uncharged or reversely charged. For the image forming apparatus / process cartridge to which the cleaning member is not applied, this toner is transported to the electrostatic latent image carrier charge imparting member portion of the next process and adhered to the contact type electrostatic latent image carrier charge imparting member portion. To do. The adhered toner becomes a cause of uneven charging when the electrostatic latent image is charged.
It is necessary to remove the adhering toner. As this method, a potential difference is generated between the electrostatic latent image carrier charge applying member and the electrostatic latent image carrier, and the toner is attached and developed on the electrostatic latent image carrier. The method of collecting by the method can be considered. In the case of this method, in order for the toner to move due to the potential difference, it is necessary that the toners have the same polarity of charge and that there is little toner of reverse polarity. Further, at the time of collection in the development process, it is necessary to have a charge equal to or higher than that of the pre-transfer toner and to have a small amount of reverse polarity toner.
As a recovery method in the development process, a method of causing a potential difference between the developing roller and the electrostatic latent image carrier to adhere to the developing roller and recovering can be considered. However, if there is a large amount of reverse polarity toner, it cannot be recovered due to the potential difference and remains on the electrostatic latent image carrier. Residual toner causes background contamination and member contamination, and image stability due to durability cannot be obtained.

JP-A-10-161400 Japanese Patent Application Laid-Open No. 11-184216 JP-A-8-227253 JP-A-8-137368

  Accordingly, the present invention has been made in view of the above problems, and the problem is that the toner remaining on the electrostatic latent image carrier is not collected and discarded, but reused, and further charged by the electrostatic latent image carrier. It is an object to provide an image forming method, a process cartridge, and an image forming apparatus that prevent contamination of the applying member, facilitate the recovery of the residual toner in the developing process, and provide excellent image stability with less durability deterioration.

The features of the present invention, which is a means for solving the above problems, are listed below.
The image forming method of the present invention, the electrostatic latent image bearing member or al rolling Utsushigo, after passing through the charge applying unit for causing again charging the toner remaining on the electrostatic latent image carried on body surface, a developing step In the image forming method recovered in the developing device in the toner composition, the toner composition has at least a pigment, a binder resin, and a layered inorganic mineral in which at least part of ions between layers is modified with organic ions, and the toner composition and / or Alternatively, a toner in which an oil phase and / or a monomer phase containing the toner composition precursor is dispersed and / or emulsified in an aqueous medium and granulated is used, and the amount of reversely charged toner after transfer and before passing through the charge applying portion is determined. When Ra, the reversely charged toner amount after passing the charging device and before passing the developing device is Rb, and the reversely charged toner amount after passing the developing device before transfer is Rc,
Rb <Rc
Rb / Ra <0.2
It said that to.
In the image forming method of the present invention, Rb and Rc are further
Rb / Rc ≦ 1
It is characterized by.
The image forming method of the present invention is further characterized in that the charge imparting portion is a conductive sheet pressed against the surface of the electrostatic latent image carrier.
The image forming method of the present invention is further characterized in that the conductive sheet is one selected from nylon, PTFE, PVDF, and urethane.
The image forming method of the present invention is further characterized in that the conductive sheet thickness is 0.05 to 0.5 mm.
The image forming method of the present invention is further characterized in that the conductive sheet resistance is 10 to 10 ⁹ Ω.
The image forming method of the present invention is further characterized in that the voltage applied to the conductive sheet is -1.4 to 0 kV.
The image forming method of the present invention is further characterized in that a nip width in which the conductive sheet is in contact with the electrostatic latent image carrier is 1 to 10 mm.
The image forming method of the present invention is further characterized in that the layered inorganic mineral is a layered inorganic mineral obtained by modifying at least part of cations between layers of the layered inorganic mineral with an organic cation.
In the image forming method of the present invention, the layered inorganic mineral obtained by modifying at least some of the ions between the layers with organic ions is one or more selected from the toner composition, an oil phase containing a toner composition precursor, and a monomer phase. It is characterized by containing 0.05 to 2% in the solid content.
The image forming method of the present invention is further characterized in that the acid value of the toner is 0.5 to 40.0 (KOHmg / g).

The process cartridge of the present invention, the electrostatic latent image bearing member or al rolling Utsushigo, after passing through the charge applying unit for causing again charging the toner remaining on the electrostatic latent image carried on body surface, in the development step In a process cartridge used for an image forming apparatus collected in a developing device, a toner composition has at least a pigment, a binder resin, and a layered inorganic mineral in which at least a part of ions between layers is modified with organic ions, and the toner A toner in which an oil phase and / or a monomer phase containing the composition and / or the toner composition precursor is dispersed and / or emulsified in an aqueous medium and granulated, and reversely charged after transfer and before passing through the charge applying portion. When the toner amount is Ra, the reversely charged toner amount after passing through the charging device and before passing through the developing device is Rb, and the reversely charged toner amount after passing through the developing device before transfer is Rc,
Rb <Rc
Rb / Ra <0.2
It characterized in that it is.
In the process cartridge of the present invention, the Rb and Rc are
Rb / Rc ≦ 1
It is characterized by being.
The process cartridge according to the present invention is further characterized in that the charge imparting portion is a conductive sheet pressed against the surface of the electrostatic latent image carrier.
The process cartridge of the present invention is further characterized in that the conductive sheet is one selected from nylon, PTFE, PVDF, and urethane.
The process cartridge of the present invention is further characterized in that the conductive sheet has a thickness of 0.05 to 0.5 mm .
The process cartridge of the present invention is further characterized in that the conductive sheet resistance is 10 to 10 ⁹ Ω.
The process cartridge of the present invention is further characterized in that the voltage applied to the conductive sheet is -1.4 to 0 kV.
The process cartridge of the present invention is further characterized in that a nip width in which the conductive sheet is in contact with the electrostatic latent image carrier is 1 to 10 mm.
The process cartridge according to the present invention is further characterized in that the layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation.
In the process cartridge of the present invention, the layered inorganic mineral obtained by modifying at least a part of ions between layers with organic ions is one or more selected from the toner composition, an oil phase containing a toner composition precursor, and a monomer phase. The solid content is 0.05 to 2%.
The process cartridge of the present invention is further characterized in that the acid value of the toner is 0.5 to 40.0 (KOH mg / g).
The image forming apparatus of the invention features by having the process cartridge.

  According to the present invention, the toner remaining on the electrostatic latent image carrier is not collected and discarded by the means for solving the problem, but reused, and further, the electrostatic latent image carrier charge imparting member is prevented from being contaminated and developed. It has become possible to provide an image forming method, a process cartridge, and an image forming apparatus that facilitate the recovery of the residual toner in the process, and that can provide excellent image stability and have little durability deterioration.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

The toner composition of the present invention has at least a pigment, a binder resin, and a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions, and the toner includes the toner composition and / or the toner composition. It is produced by dispersing and / or emulsifying an oil phase and / or a monomer phase containing a product precursor in an aqueous medium and granulating.
Further, in the present invention, the toner is used, and the reversely charged toner amount after transfer and before passing through the charge applying portion is Ra, the reversely charged toner amount after passing through the charge applying portion and before passing through the developing device is Rb, and Rb <Rc, Rb / Ra <0.2, where Rc is a reversely charged toner amount after passing through the developing device before transfer.
When Rb ≧ Rc, the recoverability in the developing device is poor and the background stains are deteriorated, but by setting Rb <Rc, they can be prevented. Further, when Rb / Ra ≧ 0.2, the development recoverability is further deteriorated, but this can be prevented by setting Rb / Ra <0.2.
Further, the Rb and Rc are set to Rb / Rc ≦ 1. If Rb / Rc is smaller than 1, toner better than the reversely charged toner amount after development is recovered, and deterioration of background contamination can be prevented.

The toner of the present invention will be described.
<Layered inorganic mineral>
The layered inorganic mineral refers to an inorganic mineral formed by superposing layers having a thickness of several nanometers, and modifying means introducing an organic ion into ions existing between the layers.
As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed, but may be modified. As a result, the hydrophilicity becomes high, and it is easily present on the surface during granulation, and is dispersed and refined to sufficiently exhibit the charge adjusting function. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 2% by mass .
The modified layered inorganic mineral used in the present invention is preferably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.
Wherein at least a portion of the layered inorganic mineral has ions of the layered inorganic mineral modified with an organic ion, the organic ion modifier quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts, the A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkyl ammonium, trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, dimethyl ammonium, Oreirubisu (2-hydroxyethyl), methyl ammonium.
Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. sulfates, sulfonic Hong salts, carboxylate or phosphate salts. A carboxylic acid having an ethylene oxide skeleton is desirable.
By at least a portion of the layered inorganic mineral is modified with organic ions, have a moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has a non-New over Tonian viscosity, irregular toner Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 2% by mass.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. In addition, as the layered inorganic mineral partially modified with an organic anion, one obtained by modifying DHA-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
Formula (1) R ₁ (OR ₂ ) _n OSO ₃ M
In the formula, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element.
By using a modified layered inorganic mineral, it has moderate hydrophobicity, and therefore tends to be present at the interface of the droplets, so that the surface is unevenly distributed and can exhibit charging properties.

<Toner resin>
There is no restriction | limiting in particular as resin for toner used by this invention, Although it can select suitably according to the objective, A styrene-acrylic-type resin, a polyester-type resin, etc. are mentioned especially suitably.
In the present invention, a polyester resin is preferably used, and there is no particular limitation on the type, and any type can be used, and several types of polyester resins may be mixed and used. Examples of the polyester resin include polycondensates of the following polyol (1) and polycarboxylic acid (2).

(About polyol)
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, etc .; bis (3-fluoro-4-hydroxyphenyl) Nyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Bis (5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene oxide) De, propylene oxide, and the like butylene oxide, etc.) adducts.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Polycarboxylic acid)
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).
Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polycarboxylic acids having 3 or more valences include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Ratio of polyol and polycarboxylic acid)
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 5 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. It is 1-1 / 1, More preferably, it is 1.3 / 1-1.02 / 1.
(Molecular weight of polyester resin)
The peak molecular weight is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate.

<Modified polyester resin>
The binder resin (A) used in the present invention may contain a modified polyester resin having a urethane or / and urea group in order to adjust viscoelasticity for the purpose of preventing offset. In the binder resin (A), the content of the modified polyester resin having urethane or / and urea groups is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having a urethane or / and urea group may be directly mixed with the binder resin (A), but from the viewpoint of productivity, a relatively low molecular weight modified polyester having an isocyanate group at the terminal. A resin (hereinafter sometimes referred to as a prepolymer) and an amine that reacts with the resin are mixed with the binder resin (A), and during the granulation / after granulation, chain elongation or / and a crosslinking reaction are carried out to produce the urethane. Alternatively, it is preferable to become a modified polyester resin having a urea group. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity in the core portion.

(Prepolymer)
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group that is further reacted with a polyisocyanate (3). . Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.
(Polyisocyanate)
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

(Ratio of isocyanate group to hydroxyl group)
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. It is. If it is less than 0.5% by mass, the offset resistance deteriorates. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.
(Number of isocyanate groups in the prepolymer)
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.
(Chain extension and / or cross-linking agent)
In the present invention, amines can be used as chain extenders and / or crosslinkers. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include the following.
Aromatic diamine (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); cycloaliphatic diamine (4,4′-diamino-3) , 3 'dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.) Examples of the polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
(Stopper)
Furthermore, if necessary, the molecular extension of the modified polyester after completion of the reaction can be adjusted by using a terminator for the chain extension and / or crosslinking reaction. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).
(Ratio of amino group to isocyanate group)
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

<Colorant>
As the colorant of the present invention can use any known dyes and pigments such as carbon black, nigrosine dye, iron black, Naphthol Yellow S, Hansa Yellow (10G, 5G, G), Kado Miu Muiero, 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, Anse La Giang yellow BGL, isoindolinone yellow, red iron oxide, red lead, Namarishu, Kado Miu Mureddo, Kado Miu-time Ma Curie red, antimony vermilion, permanent Red 4R, Para Red, phi Sayred, Parachlor Ortonito Aniline red, Li Saul Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL , F4RH), fast scarlet VD, bell cans Fast Rubin B, brilliant scarlet G, Lithol Rubine GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, Riazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalo Cyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

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

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

<Release agent>
Further, as the mold release agent used in the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax. Etc. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
In the present invention, the wax content in the toner is more preferably 5 to 15% by mass with respect to 100% by mass of the resin component. If the amount of wax with respect to the total amount of toner is less than 5%, the releasing effect by the wax may be lost, and the margin for preventing offset may be lost. On the other hand, if it exceeds 15%, the wax melts at a low temperature, so it is easily affected by thermal energy and mechanical energy. It may adhere to the image carrier and generate image noise. Further, the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax can fix the toner at a low temperature of 65 to 115 ° C., but if the melting point is less than 65 ° C., the fluidity becomes poor. When the temperature is higher than 115 ° C., the fixability tends to deteriorate.

<Charge control agent>
The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of 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-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

<External additive>
(Inorganic fine particles)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, complex oxides such as silicon oxide / magnesium oxide and silicon oxide / aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, nitriding Silicon etc. can be mentioned.
(Polymer fine particles)
Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, and nylon, and thermosetting resin Examples include polymer particles.
(Surface treatment of external additives)
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
(Cleaning aid)
Examples of the cleaning property improving agent for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles. And polymer fine particles produced by soap-free emulsion polymerization such as polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Toner production method>
When the toner material is emulsified or dispersed in the aqueous medium using the liquid containing the toner material, the liquid containing the toner material is preferably dispersed in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion is easier when the dispersion temperature is higher.
The method for forming the toner base particles can be appropriately selected from known methods. Specifically, a method for forming toner base particles using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like, a method for forming toner base particles while producing an adhesive substrate, etc. Among these, a method of forming toner base particles while producing an adhesive substrate is preferable. Here, the adhesive base material is a base material having adhesiveness to a recording medium such as paper.
A method of forming toner base particles while producing an adhesive substrate is a method in which a toner material contains a compound having an active hydrogen group and a polymer having reactivity to the active hydrogen group, and is active in an aqueous medium. This is a method of forming toner base particles while producing an adhesive substrate by reacting a compound having a hydrogen group with a polymer having reactivity with an active hydrogen group. In addition, the adhesive base material may further contain a known binder resin.
The toner thus obtained preferably contains a colorant, and may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.
The mass average molecular weight of the adhesive substrate is preferably 3000 or more, more preferably 5000 to 1000000, and particularly preferably 7000 to 500000. When the mass average molecular weight is less than 3000, the hot offset resistance may be lowered.
The production method of the toner of the present invention is not limited to this, but is preferably produced by the following production method.
In the toner production method of the present invention, a binder resin having at least an aromatic group-containing polyester skeleton, a colorant and a release agent are dissolved or dispersed in an organic solvent, and then the dissolved or dispersed material is dispersed in an aqueous medium. At least a step of dispersing and granulating.

More specifically, it is as follows.
<Granulation process>
(Organic solvent)
As an organic solvent for dissolving or dispersing a binder resin having an aromatic group-containing polyester skeleton, a colorant and a release agent, the Hansen solubility parameter described in Volume 2, Section VII of “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE It is preferably 19.5 or less, and preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin, the colorant and the release agent may be dissolved or dispersed at the same time. Usually, each of them is dissolved or dispersed alone, and the organic solvents used at that time may be different or the same. The same is preferable considering the above.

(Dissolution or dispersion of binder resin having aromatic group-containing polyester skeleton)
The resin concentration or concentration of the binder resin having an aromatic group-containing polyester skeleton is preferably about 40% to 80%. If the concentration is too high, it will be difficult to dissolve or disperse, and the viscosity will be too high to handle. On the other hand, if the density is too low, the amount of toner produced decreases. When mixing a modified polyester resin having an isocyanate group at the terminal with a binder resin having an aromatic group-containing polyester skeleton, it may be mixed in the same solution or dispersion, or separately prepared in a solution or dispersion. However, considering the respective solubility and viscosity, it is preferable to prepare separate solutions or dispersions.
(Dissolution or dispersion of colorant)
The colorant may be dissolved or dispersed alone, or may be mixed in the solution or dispersion of the polyester resin. If necessary, a dispersion aid or a polyester resin may be added, or the master batch may be used.
(Dissolution or dispersion of release agent)
When dissolving or dispersing wax as a release agent, when using an organic solvent in which wax does not dissolve, it is used as a dispersion, but the dispersion is prepared by a general method. That is, an organic solvent and wax may be mixed and dispersed with a disperser such as a bead mill. Further, after mixing the organic solvent and the wax, it is sometimes possible to shorten the dispersion time by once heating to the melting point of the wax, cooling with stirring and then dispersing with a disperser such as a bead mill. In addition, a plurality of waxes may be mixed and used, or a dispersion aid or a polyester resin may be added.

(Aqueous medium)
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Furthermore, an organic solvent having a Hansen solubility parameter of 19.5 or less used in the oil phase may be mixed, and preferably the addition amount in the vicinity of the saturation amount with respect to water increases the emulsification or dispersion stability of the oil phase. it can. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The amount of the aqueous medium used relative to 100 parts by mass of the toner composition is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. Moreover, when it exceeds 2000 mass parts, it is not economical.
(Inorganic dispersant and organic resin fine particles)
When the dissolved or dispersed toner composition is dispersed in the aqueous medium, by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance, the particle size distribution is sharpened and the dispersion is reduced. It is preferable in terms of stability. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin for forming the organic resin fine particles, any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin. Includes vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

(Method for dispersing organic resin fine particles in water)
The method of making the resin into an aqueous dispersion of fine organic resin particles is not particularly limited, and examples thereof include the following (a) to (h).
(A) In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material .
(B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. .) A method in which a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.
(D) A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) can be used as a mechanical rotary type or jet type resin. A method in which resin fine particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method in which resin fine particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of an appropriate dispersant.
(F) A solvent is added to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin fine particles are precipitated by cooling the resin solution previously dissolved in a solvent by heating, and then the solvent is removed to obtain resin fine particles, which are then dispersed in water in the presence of a suitable dispersant. Method.
(G) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method of dispersing in an aqueous medium in the presence of an appropriate dispersant and removing the solvent by heating or decompression.
(H) In a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. A method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier.

(Surfactant)
Further, a surfactant or the like can be used as necessary in order to emulsify and disperse the oily phase containing the toner composition in the aqueous medium. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.
Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

(Protective colloid)
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methyl alcohol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

(Desolation)
In order to remove the organic solvent from the obtained emulsified dispersion, a known method can be used. For example, a method can be employed in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

<Extension or / and cross-linking reaction>
For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with the polyester resin are added, the toner composition is placed in an aqueous medium. Before dispersion, amines may be mixed in the oil phase, or amines may be added to the aqueous medium. The time required for the above reaction is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. This reaction may be performed before the fine particle adhesion step, or may be performed simultaneously during the fine particle adhesion step. Further, it may be after the fine particle adhesion step is completed. Moreover, a well-known catalyst can be used as needed.

<Washing and drying process>
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying a mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. Henschel mixer (made by Mitsui Mining Co., Ltd.), super mixer (made by Kawata Co., Ltd.), Ong mill (made by Hosokawa Micron Co., Ltd.) and I-type mill (made by Nippon Pneumatic Co., Ltd.) were modified to reduce the pulverization air pressure. Examples thereof include an apparatus, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

<Process cartridge>
The developer of the present invention can be used in, for example, an image forming apparatus provided with a process cartridge as shown in FIG. The present invention is an image forming method for performing image recording without using an apparatus for cleaning residual toner after transfer. By using this cleanerless image forming method, the cleaning device can be excluded, and the toner remaining on the electrostatic latent image carrier 1 can be used again at the time of image formation. This is an extremely useful technique as an image forming device that can be softened.
Further, these cleanerless image forming methods have an aspect that the apparatus can be miniaturized because no storage container is used. That is, it is possible to satisfy the need for downsizing of the apparatus, which is one of the demands for printers and copying machines using the electrophotographic system. Therefore, the cleanerless image forming method is a very effective technique that can cope with environmental loads and contribute to downsizing of the image forming apparatus.

In the present invention, the electrostatic latent image carrier 1, the electrostatic latent image charging means 5, the developing means 6, and the electrostatic latent image carrier 1 remain on the surface of the electrostatic latent image carrier 1 after being transferred to the next process. Among the components such as the charging unit 3 for charging the toner again, a plurality of components are integrally coupled as a process cartridge, and this process cartridge is formed into an image such as a copying machine or a printer. It is configured to be detachable from the apparatus main body. In particular, the charging member 3 is integrally supported with the electrostatic latent image carrier 1 and is detachably formed with respect to the image forming apparatus main body. In addition, the electrostatic latent image charging unit 5 and the developing unit 6 are included. It may be configured.
The process cartridge shown in FIG. 1 remains on the surface of the electrostatic latent image carrier 1 after being transferred from the electrostatic latent image carrier 1, the electrostatic latent image charging means 5, and the electrostatic latent image carrier 1 to the next process. The charging unit 3 and the developing unit 6 are provided for charging the toner again.
In operation, the electrostatic latent image carrier 1 is rotationally driven at a predetermined peripheral speed. In the rotating process, the electrostatic latent image carrier 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 5, and then image exposure from image exposure unit such as slit exposure or laser beam scanning exposure is performed. The electrostatic latent image is sequentially formed on the peripheral surface of the electrostatic latent image carrier 1 in this way, and the formed electrostatic latent image is then developed with toner by the developing means 6, and the developed toner image is The transfer unit 7 sequentially transfers the image to the transfer material fed from the paper supply unit between the electrostatic latent image carrier 1 and the transfer unit 7 in synchronization with the rotation of the electrostatic latent image carrier 1. The transfer material that has received the image transfer is separated from the surface of the electrostatic latent image carrier 1 and introduced into the image fixing means to be fixed, and printed out as a copy (copy) or print (print). . The surface of the electrostatic latent image carrier 1 after the image transfer is charged to recharge the toner remaining on the surface of the electrostatic latent image carrier 1 after transfer from the electrostatic latent image carrier 1 to the next process. The transfer residual toner is recharged by 3 and passes through the electrostatic latent image carrier charging portion, collected in the developing process, and repeatedly used for image formation.

<Charging imparting member>
The charge imparting member 3 for recharging the toner remaining on the surface of the electrostatic latent image carrier 1 after transfer from the electrostatic latent image carrier 1 to the next process is insulative in consideration of toner adhesion. Since adhesion due to charge-up occurs, it is preferably conductive.
The resistance is preferably 10 to 10 ⁹ Ω. Further, examples of the shape include a roller, a brush, a sheet, and the like, and more preferably, a sheet configuration is preferable in consideration of resetting property of attached toner.
The charge imparting member is preferably a sheet selected from nylon, PTFE, PVDF, and urethane, and more preferably PTFE or PVDF from the viewpoint of toner chargeability.
When the charge imparting member is a conductive sheet, the thickness is preferably 0.05 to 0.5 mm from the viewpoint of contact pressure with the electrostatic latent image carrier. In the case where the charge imparting member is a conductive sheet, the nip width in contact with the latent image carrier is preferably 1 to 10 mm from the viewpoint of contact time when toner is charged. The voltage applied to the charge imparting member is preferably -1.4 to 0 kV from the viewpoint of imparting toner charge.

  Toner analysis and evaluation were performed as follows. Although the following was evaluated as a one-component developer, the toner of the present invention can also be used as a two-component developer by using a suitable external addition process and a suitable carrier.

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

(Average circularity)
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing 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. The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle.
This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. As a specific measurement method, 0.1 to 0.5 mL of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant in 100 to 150 mL of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μL. .

(Molecular weight)
The molecular weights of the polyester resin and vinyl copolymer resin used were measured under the following conditions by ordinary GPC (gel permeation chromatography).
・ Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M x 3
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 0.35 mL / min ・ Sample: 0.01 mL injection of a sample having a concentration of 0.05 to 0.6% A molecular weight calibration curve prepared by a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions Was used to calculate the weight average molecular weight Mw. As the monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 100 to 7.5 × 1000000 were used.

(Glass transition point)
For measuring the glass transition point of the polyester resin or vinyl copolymer resin to be used, for example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) After heating to 150 ° C. for 10 minutes, leave the sample at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, heat it again to 150 ° C. at a heating rate of 10 ° C./min, It can be determined at the intersection with the tangent of the curved portion showing the glass transition.
(Particle size)
The particle size of the vinyl copolymer resin fine particles used can be measured as a dispersion using a measuring device such as LA-920 (Horiba Seisakusho) or UPA-EX150 (Nikkiso).

(Reverse polarity toner amount)
Performing reverse polarity toner amount measurement on the electrostatic latent image bearing member in each step after the initial stage and 1000 sheets printed by a laser Doppler method Espert analyzer using (KK Hosokawa micron). An example of the charge amount distribution measurement result is shown in FIG.
(1) Measurement conditions FIELD VOLTAGE (measurement unit voltage): 0.1 kV
Particle Density: 1.1
GAS SUPPLY (supply part injection N ₂ pressure): 0.03 Mpa
Measuring unit suction flow rate: 0.35 L / min
Number of measurement: 3000 (2) Measurement method (2) -1. Ra measurement A4 Vertical solid black printing is performed, and the machine is forcibly stopped at the timing when about 5 cm is transferred from the front end. The charge amount distribution of the toner remaining on the electrostatic latent image carrier within 5 cm from the contact portion between the electrostatic latent image carrier and the transfer member is measured.
(2) -2. Rb measurement A4 A black and white printing is performed on the entire vertical surface, and after the transfer, the machine is forcibly stopped at a timing before the toner remaining on the electrostatic latent image carrier reaches the electrostatic latent image carrier charging member. The charge amount distribution of the toner remaining on the electrostatic latent image carrier within 5 cm from the electrostatic latent image carrier charging member is measured.
(2) -3. Rc measurement A4 Vertically whole surface printing is performed, and the machine is forcibly stopped at the timing of developing about 5 cm on the electrostatic latent image carrier. The charge amount distribution of the toner on the electrostatic latent image carrier within 5 cm from the contact portion between the electrostatic latent image carrier and the developing member and before the transfer member contact portion is measured.

<Evaluation method>
(Cleanerless suitability evaluation: development recovery)
The charging roller of Ricoh's IPSIO CX3000 is replaced with a brush roller, the electrostatic latent image carrier cleaning blade is removed, and a conductive sheet is placed in contact with the surface of the electrostatic latent image carrier. Such an electrostatic latent image carrier cleanerless system was adopted. In monochrome mode, a predetermined print pattern with a B / W ratio of 6% was continuously printed in an N / N environment (23 ° C., 45%) for 1000 sheets. At this time, the development recovery performance was evaluated as a rank as a cleaner-less aptitude evaluation.
As for the development recoverability, the toner remaining on the photosensitive member at the end of printing 1000 sheets was peeled off with a tape, and L * was measured with a spectral densitometer Xrite 939.
◎: 90 or more ○: 85 or more and less than 90 Δ: 80 or more and less than 85 ×: less than 80

(Example)
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Parts” means all parts by mass.
<Synthesis of polyester>
(Polyester 1) In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 553 parts of bisphenol A ethylene oxide 2-mole adduct, 196 parts of bisphenol A propylene oxide 2-mole adduct, 220 parts of terephthalic acid, adipic acid 45 parts and 2 parts of dibutyltin oxide were added, reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg, and then 46 parts of trimellitic anhydride was added to the reaction vessel at 180 ° C. Reaction was performed at normal pressure for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 220, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 13.
<Synthesis of prepolymer>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.
<Synthesis of master batch>
Carbon black (Cabot Co., Ltd. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

Example 1
<Preparation of pigment / wax dispersion (oil phase)>
378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9), and 1450 parts of ethyl acetate were charged into a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 655 parts of a 65% ethyl acetate solution of [Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. Ethyl acetate was added and adjusted so that the solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.
<Preparation of aqueous phase>
953 parts of ion-exchanged water, 88 parts of a 25% by weight aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl 90 parts of a 48.5% aqueous solution of sodium diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated [Aqueous Phase 1].
<Emulsification process>
[Pigment / Wax Dispersion 1] 967 parts, 2% of layered inorganic mineral shown in Table 1 (in terms of toner solid content) is added, 6 parts of isophorone diamine as amines, TK homomixer (manufactured by Tokushu Kika) After mixing at 5,000 rpm for 1 minute, add 137 parts of [Prepolymer 1], mix with TK homomixer (manufactured by Special Machine) for 1 minute at 5,000 rpm, and then add 1200 parts of [Aqueous Phase 1]. In addition, the mixture was mixed with a TK homomixer at a rotational speed of 8,000 to 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 1].
<From washing to drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12 and the average circularity was 0.973. Next Ide, and 0.5 part of hydrophobic silica 100 parts of this mother toner, a mixture of 0.5 parts of hydrophobized titanium oxide using a HENSCHEL MIXER to obtain [developer 1] of the present invention.

(Examples 2 to 10)
Developers of Examples 2 to 10 were obtained in the same manner as in Example 1 except that the layered inorganic mineral species and amount of Example 1 were changed as shown in the toner evaluation results in Table 2.

(Example 11)
<Preparation of Colorant Dispersion 1>
125 parts of carbon black (manufactured by Degussa: Printex 35), 18.8 parts of Ajisper PB821 (manufactured by Azinomoto Finetech), 356.2 parts of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade), Ultraviscomyl ( [Imex Co., Ltd.] was used for dissolution / dispersion to prepare [Colorant Dispersion Liquid 1] in which a colorant (black pigment) was dispersed.
<Preparation of mold release agent dispersion (wax component A)>
Carnauba wax (melting point: 83 ° C., acid value 8 mg KOH / g, saponification value 80 mg KOH / g) 30 parts, ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade) 270 parts, Ultraviscomil (made by Imex Corporation) Was used for wet pulverization to prepare [Mold release agent dispersion 1].
<Preparation of layered inorganic mineral dispersion 1 modified with organic cations>
30 parts of Clayton APA (manufactured by Southern Clay Products), 270 parts of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd .: special grade), and the above are wet-ground using ultraviscomyl (manufactured by IMEX), and [layered inorganic mineral Dispersion 1] was prepared.
<Preparation of liquid A>
Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylene oxide adduct, terephthalic acid derivative (Mw 50,000, Mn 3,000, acid value 15 mg KOH / g, hydroxyl value 27 mg KOH / g Tg 55 ° C., softening point 112 ° C.) 350 Parts, [Colorant dispersion 1] 245 parts, [Releasing agent dispersion 1] 800 parts, [Layered inorganic mineral dispersion 1] 400 parts, Hydrophobic silicon oxide fine particles (Aerosil R972) 17.8 parts, The above was mixed and stirred well until uniform, and this liquid was designated as [A liquid].
<Preparation of liquid B>
100 parts of calcium carbonate dispersion in which 40 parts of calcium carbonate fine particles are dispersed in 60 parts of water, 200 parts of 1% aqueous solution of Serogen BS-H (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 157 parts of water K. The mixture was stirred for 3 minutes using a homodisper fmodel (manufactured by Primix). This liquid was designated as [B liquid].
<Create toner>
T.A. K. Using a homomixer mark2 fmodel (manufactured by Primix), 345 parts of the solution B and 250 parts of the solution A were stirred at 10,000 rpm for 2 minutes to suspend the mixed solution, and then propeller type at room temperature and normal pressure for 48 hours. The solvent was removed by stirring with a stirrer. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The average particle size of the toner was 6.2 μm.

(Example 12)
5 parts of Na ₃ PO ₄ was introduced into 500 parts of ion-exchanged water, heated to 60 ° C., and then stirred with a CLEARMIX high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s). To this, an aqueous solution containing 2 parts of CaCl ₂ dissolved in 15 parts of ion-exchanged water was quickly added to obtain an aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
On the other hand, 85 parts of polymerizable monomer styrene, 20 parts of n-butyl acrylate, colorant C.I. I. Pigment Blue 15: 3 7.5 parts, charge control agent E-88 (manufactured by Orient Chemical Co., Ltd.) 1 part, polar resin saturated polyester 5 parts acid value 10 mgKOH / g, peak molecular weight: 7,500), release agent ester 15 parts of wax (maximum endothermic peak temperature in DSC 72 ° C.), 2 parts of Kraton APA (manufactured by Southern Clay Products) are heated to 60 ° C. and stirred to uniformly dissolve each material in the polymerizable monomer or Dispersed. To this was added 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator to prepare a polymerizable monomer composition.
The polymerizable monomer composition is introduced into the aqueous dispersion medium, and then at a temperature of 60 ° C. and N ₂ atmosphere for 15 minutes with a CLEARMIX high-speed stirrer (manufactured by M Technique, peripheral speed 22 m / s). Stirring to produce particles of the polymerizable monomer composition in the aqueous dispersion medium. After the dispersion, the stirring apparatus was stopped and introduced into a polymerization apparatus equipped with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.). In the polymerization apparatus 11, the polymerizable monomer was reacted for 5 hours while stirring the stirring blade at the maximum peripheral speed of stirring: 3 m / s in a N ₂ atmosphere at a temperature of 60 ° C. Thereafter, the temperature was raised to 80 ° C., and the polymerizable monomer was further reacted for 5 hours. After completion of the polymerization reaction, the toner was obtained by washing with water, drying and classification. The average particle size of the toner was 5.8 μm.

(Comparative Examples 1-3)
Developers of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except that the layered inorganic mineral species and amount of Example 1 were changed as shown in the toner evaluation results in Table 2.
The resin physical properties of the highly polar resins produced above are listed in Table 1 and the properties and evaluation results of the developers produced in Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 1. They are summarized in each.

It is a figure which shows the process cartridge of this invention. It is a figure which shows the example of a charge amount distribution measurement result.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrostatic latent image carrier 3 Charging part 5 Electrostatic latent image charging means 6 Developing means 7 Transfer means

Claims (23)

The electrostatic latent image bearing member or al rolling Utsushigo, after passing through the charge applying unit for causing again charging the toner remaining on the electrostatic latent image carried on body surface, the image to be collected in the developing apparatus in the developing step In the forming method,
The toner composition has at least a pigment, a binder resin, and a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions,
Using a toner that is granulated by dispersing and / or emulsifying an oil phase and / or a monomer phase containing the toner composition and / or the toner composition precursor in an aqueous medium,
The reversely charged toner amount after transfer and before passing through the charge applying portion is Ra, the reversely charged toner amount after passing through the charge applying portion and before passing through the developing device is Rb, and the reversely charged toner after passing through the developing device before transfer. When the amount is Rc,
Rb <Rc
Rb / Ra <0.2
And an image forming method. The image forming method according to claim 1,
Rb and Rc are
Rb / Rc ≦ 1
And an image forming method. The image forming method according to claim 1 or 2,
The image forming method, wherein the charging portion is a conductive sheet pressed against the surface of the electrostatic latent image carrier. The image forming method according to claim 3.
The image forming method, wherein the conductive sheet is one selected from nylon, PTFE, PVDF, and urethane. The image forming method according to claim 3 or 4,
The conductive sheet thickness is 0.05 to 0.5 mm. The image forming method according to claim 3, wherein:
The conductive sheet resistance is 10 to 10 ⁹ Ω. The image forming method according to any one of claims 3 to 6,
The image forming method, wherein a voltage applied to the conductive sheet is −1.4 to 0 kV. The image forming method according to claim 3,
The image forming method, wherein a nip width in which the conductive sheet is in contact with the electrostatic latent image carrier is 1 to 10 mm. The image forming method according to claim 1,
The layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation. The image forming method according to claim 1,
A layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is 0.05 to 1.5 in a solid content in one or more selected from the toner composition, an oil phase containing a toner composition precursor, and a monomer phase. An image forming method comprising 2%. The image forming method according to claim 1,
The acid value of the toner is 0.5 to 40.0 (KOH mg / g). The electrostatic latent image bearing member or al rolling Utsushigo, after passing through the charge applying unit for causing again charging the toner remaining on the electrostatic latent image carried on body surface, the image to be collected in the developing apparatus in the developing step In a process cartridge used for a forming apparatus,
The toner composition has at least a pigment, a binder resin, and a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions,
A toner that is granulated by dispersing and / or emulsifying an oil phase and / or a monomer phase containing the toner composition and / or the toner composition precursor in an aqueous medium;
The reversely charged toner amount after transfer and before passing through the charge applying portion is Ra, the reversely charged toner amount after passing through the charge applying portion and before passing through the developing device is Rb, and the reversely charged toner after passing through the developing device before transfer. When the amount is Rc,
Rb <Rc
Rb / Ra <0.2
A process cartridge characterized by The process cartridge according to claim 12,
Rb and Rc are
Rb / Rc ≦ 1
A process cartridge characterized by The process cartridge according to claim 12 or 13,
The process cartridge, wherein the charging unit is a conductive sheet pressed against the surface of the electrostatic latent image carrier. The process cartridge according to claim 14, wherein
The process cartridge is characterized in that the conductive sheet is one selected from nylon, PTFE, PVDF, and urethane. The process cartridge according to claim 14 or 15,
The conductive sheet has a thickness of 0.05 to 0.5 mm. The process cartridge according to any one of claims 14 to 16,
The conductive sheet resistance is 10 to 10 ⁹ Ω. The process cartridge according to any one of claims 14 to 17,
A process cartridge in which a voltage applied to the conductive sheet is -1.4 to 0 kV. The process cartridge according to any one of claims 14 to 18,
A process cartridge, wherein the conductive sheet is in contact with the electrostatic latent image carrier and has a nip width of 1 to 10 mm. The process cartridge according to any one of claims 12 to 19,
The layered inorganic mineral is a layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation. The process cartridge according to any one of claims 12 to 20,
A layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is 0.05 to 1.5 in a solid content in one or more selected from the toner composition, an oil phase containing a toner composition precursor, and a monomer phase. A process cartridge characterized by being 2%. The process cartridge according to any one of claims 12 to 21,
An acid value of the toner is 0.5 to 40.0 (KOHmg / g). An image forming apparatus comprising the process cartridge according to claim 12.

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