JP2008225422A - Toner for electrostatic charge image development and manufacturing method, and image forming method using the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner excellent in charging property, environmental stability and durability stability and giving an excellent printed material causing neither scumming nor sticking, and to provide a process cartridge for the toner. <P>SOLUTION: The toner comprises at least a colorant, a binder resin, a release agent and a modified layered inorganic mineral prepared by modifying at least a part of interlayer ions in the layered inorganic mineral with an organic ion, and is characterized in that: the volume average particle diameter of the toner is 4 to 8 μm; and in a reflective electron image of the toner cross section by thermal FE SEM, the proportion of the area occupied by the modified layered inorganic mineral in a region at 50 nm from the toner rim is not less than 70%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and an electrophotographic developing apparatus using the toner. More specifically, the present invention relates to an electrophotographic toner used in a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system, and an image forming method.

  In recent years, higher performance of printers, in particular, full-color printers have been improved in speed, life, image quality, and the like, and the required performance for toner has also increased. In particular, for speeding up the printer, the chargeability and stability of the toner are emphasized, and many studies have been made on charge control agents as measures for improving them.

In general, it is considered that the charge control agent has a large influence on the surface of the toner, and a large amount of charge control agent is added to control the charge of the toner, but the thermoplastic resin as the binder resin is added. In the so-called pulverization method in which a toner is prepared by melt-kneading a mixture to which a colorant and an additive used as needed are melt-kneaded, and then pulverizing and classifying, (1) it is the limit to reduce the particle size However, it is impossible to control the arrangement of the materials in the particles, although (2) kneading ⇒ pulverization allows uniform dispersion in each particle. (3) When the amount of the charge control agent is increased for imparting charging property, a side effect on filming / fixing property occurs. A malfunction occurred.
In recent years, modified layered inorganic minerals in which some of the ions present between layers in layered inorganic minerals are modified with organic ions have been proposed as charge control agents, which also have the above-mentioned problems (Patent Documents 1 to 3). 4).

JP-T-2003-515795 Special table 2006-500605 gazette JP-T-2006-503313 Special table 2003-202708 gazette

  The present invention has been made in view of the above problems, and provides a toner and a toner process cartridge that are excellent in chargeability, environmental stability, and durability stability, and that can provide a good printed matter that does not cause scumming or sticking. can do.

  As a result of intensive studies to solve the above-described problems, the present inventors have completed the present invention. According to the present invention, the following toner and image forming apparatus are provided.

(1) In a toner composed of a modified layered inorganic mineral obtained by modifying at least part of ions between layers of a colorant, a binder resin, a release agent, and a layered inorganic mineral with an organic ion, the volume average particle diameter is 4 to 4. A toner having a surface area of 50 μm and an area occupied by the modified layered inorganic mineral in a region 50 nm from the peripheral edge of the toner in a reflected electron image by thermal FE SEM of the cross section of the toner is 70% or more.
(2) The toner according to (1), wherein the modified layered inorganic mineral is a modified layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation. .
(3) The toner disperses and / or disperses, in an aqueous medium, a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor. Alternatively, the toner according to (1) or (2), wherein the toner is obtained by emulsifying and granulating.
(4) In the solution or dispersion, 0.05 to 2% by mass of a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is contained in the solid content of the solution or dispersion. The toner according to (3) above, wherein
(5) The toner according to any one of (1) to (4) above, wherein the toner is obtained by removing an organic solvent after forming particles in an aqueous medium.
(6) The toner according to any one of the above (1) to (5), wherein the toner is obtained by subjecting the toner to a washing treatment with a washing aqueous medium after particle formation in an aqueous medium and then a drying treatment. toner.
(7) The toner according to any one of (1) to (6), wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher.
(8) The toner according to any one of (1) to (7) above, wherein the binder resin described above contains a polyester resin extended by urethane or / and urea bonds.
(9) The toner according to (8), wherein the polyester resin described above contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at the terminal and amines.
(10) The toner according to any one of (1) to (9), wherein the toner has a circularity of 0.95 or more and less than 0.99.
(11) The above-mentioned (1), wherein the release agent contains one or more kinds selected from the group consisting of paraffins, synthetic esters, polyolefins, carnauba wax, and rice wax. The toner according to any one of to (10).
(12) The toner according to any one of (1) to (11), wherein the toner contains a charge control agent.
(13) The toner according to any one of (1) to (12), wherein the toner is a non-magnetic one-component developing toner.
(14) An image forming apparatus using the nonmagnetic one-component developing toner described in (13).
(15) The image forming apparatus according to (14), wherein the image forming apparatus is an apparatus that forms a multicolor image.
(16) The image forming apparatus as described in (14) or (15) above, wherein the image forming apparatus has an endless intermediate transfer means.
(17) The image forming apparatus as described in any one of (14) to (16) above, wherein the image forming apparatus is not provided with a blade as a residual toner cleaning unit in the photoreceptor or / and the intermediate transfer unit.
(18) The image forming apparatus according to any one of (14) to (16), wherein the image forming apparatus includes a blade cleaning unit.
(19) The image forming apparatus according to any one of (14) to (18), wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device.
(20) The image forming apparatus according to any one of (14) to (18), wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device.
(21) The image forming apparatus according to any one of (14) to (18), wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to a fixing member.
(22) A toner container filled with the toner according to any one of (1) to (13) above.
(23) A toner container filled with the nonmagnetic one-component developing toner according to (13).
(24) In the process cartridge that integrally supports the developing unit and at least one unit selected from the group consisting of an image carrier, a charging unit, and a cleaning unit, and is detachable from the main body of the image forming apparatus, the development The means holds the toner, and the toner is the toner according to any one of the above (1) to (13).

  According to the present invention, it is possible to provide a toner and a toner process cartridge that are excellent in chargeability, environmental stability, and durability stability, and that can provide a good printed matter that does not cause scumming or sticking.

The toner of the present invention comprises a modified layered inorganic mineral obtained by modifying at least part of ions between layers of a colorant, a binder resin, a release agent, and a layered inorganic mineral with organic ions. The volume average particle diameter is 4 to 8 μm, and the ratio of the area occupied by the modified layered inorganic mineral in the region 50 nm from the peripheral edge of the toner is 70% or more in the reflected electron image by thermal FE SEM of the toner cross section. .
As described above, in the reflected electron image by thermal FE-SEM of the cross section of the toner, the modified layered inorganic mineral occupies 70% or more area in the region of 50 nm from the peripheral edge of the toner, so that the modified layered inorganic mineral is unevenly distributed on the toner surface. In addition, it is excellent in chargeability, environmental stability and durability stability, and has the effect of preventing soiling and sticking.
Modified layered inorganic minerals, which have good wettability to water, are modified with organic ions to have moderate hydrophobicity. When granulated in an aqueous medium, the liquid droplets are dispersed in the aqueous medium. It tends to exist at the interface and prevents the wax from being exposed to the surface by being unevenly distributed on the surface of the obtained toner, so that the wax component adheres to other members such as a photoconductor during long-term printing, thereby degrading the image quality. It is thought to prevent this.
The area of the toner surface area covered with the modified layered inorganic mineral in the vicinity of the surface can be measured by a FE-SEM (Field Emission Scanning Electron Microscope) described later.

  Below, each component which comprises the toner of this invention is demonstrated.

<Modified layered inorganic mineral>
A layered inorganic mineral refers to an inorganic mineral made up of layers of several nanometers in thickness, and to modify means to introduce organic ions into ions existing between the layers. This is called intercalation in a broad sense.
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. By doing so, it is easily deformed during granulation, dispersed and refined, and the charge adjusting function is fully exhibited. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 5.0% by weight.

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.
Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. Quaternary alkyl ammonium salts are preferred. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  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, sulfonates, carboxylates or phosphates are raised. A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed 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 0.1 to 5% by weight.
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 organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL (above, Quartium 18 bentonite such as Southern Clay, Inc .; Steallarconium bentonite such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (above, manufactured by Southern Clay), etc .; Clayton HT And quaternium 18 / benzalkonium bentonite such as Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-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) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
Formula (1) R ₁ (OR ₂ ) _n OSO ₃ M
[Wherein, 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]

  The kneaded composite of the modified layered inorganic mineral and the binder resin, that is, the masterbatch can be obtained by mixing and kneading the binder resin and the layered inorganic mineral modified with organic ions under high shear force to obtain a masterbatch. . At this time, an organic solvent can be used to enhance the interaction between the modified layered inorganic mineral and the binder resin. Also, a so-called flushing method is a method in which an aqueous paste containing the modified layered inorganic mineral and water is mixed and kneaded together with a resin and an organic solvent, and the modified layered inorganic mineral is transferred to the resin side to remove moisture and organic solvent components. Also, since the wet cake 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.

In the kneaded composite of the modified layered inorganic mineral and the binder resin, that is, the master batch, the volume average particle diameter Dv of the modified layered inorganic mineral is preferably 0.1 μm to 0.5 μm. When the volume average particle diameter Dv exceeds 0.5 μm, the effect on the toner shape and toner charging performance is lowered.
The modified layered inorganic mineral is preferably contained in the toner in an amount of 0.1 to 5% by weight. If it is less than 0.1% by weight, the effect on the toner shape and the toner charging performance is lowered, and if it exceeds 5% by weight, the fixing performance is deteriorated.
By using the modified layered inorganic mineral, it has moderate hydrophobicity, and therefore tends to be present at the interface of the droplets, so that it is unevenly distributed on the surface and can exhibit charging properties.

<Binder resin>
The <binder resin used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are styrene-acrylic resins and polyester resins.
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 trivalent 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, polyvalent polycarboxylic acids having 3 or more valences are 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 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

(Molecular weight of polyester resin)
The peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 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 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. The content of the modified polyester resin having a urethane or / and urea group is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less in the binder resin. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having urethane or / and urea groups may be directly mixed with the binder resin, but from the viewpoint of manufacturability, a relatively low molecular weight modified polyester resin having an isocyanate group at the terminal (hereinafter referred to as “polyester resin”) And an amine that reacts with the binder resin is mixed with the binder resin, and during the granulation / after granulation, chain extension or / and cross-linking reaction is carried out to form the urethane or / and urea group. It is preferable to have a modified polyester resin. 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 further reacted with the 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.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam 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 weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the offset resistance deteriorates. On the other hand, if it exceeds 40% by weight, 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 extension and / or crosslinking agents. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino groups B1 to B5 blocked (B6).
Examples of the diamine (B1) include the following.
Aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.);
Alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.);
And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.) Examples of the trivalent or higher polyamine (B2) include diethylenetriamine, triethylenetetramine, and the like. It is done.
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, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for the chain extension and / or crosslinking reaction, if necessary. 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, all known dyes and pigments can be used. 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, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on 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-malein 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. In addition, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Release agent>
As the 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, sasol wax, etc.); carbonyl group-containing wax, etc. Can be mentioned. 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 trimellitate, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) ); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

  In the present invention, it is more preferable that the wax content in the toner is 5 to 15% by weight with respect to 100% by weight 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 phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical 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 proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium zinc titanate, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, composite oxides such as silicon oxide / magnesium oxide and silicon oxide / aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride And so on.

(Polymer fine particles)
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins 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 improver 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 weight 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 weight 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.
The method for producing the toner of the present invention comprises dissolving or dispersing a binder resin, a highly polar resin, a colorant and a release agent having at least an aromatic group-containing polyester skeleton in an organic solvent, and then dissolving or dispersing the binder or resin. At least a step of dispersing in an aqueous medium 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)
It is preferable that the binder resin having an aromatic group-containing polyester skeleton has a resin concentration of about 40% to 80%. If the concentration is too high, it becomes difficult to dissolve or disperse, and the viscosity is too high to handle. On the other hand, if the density is too low, the amount of toner produced decreases. When the modified polyester resin having an isocyanate group at the terminal is mixed with the binder resin having an aromatic group-containing polyester skeleton, it may be mixed in the same solution or dispersion, or separately prepared in the 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 with the polyester resin dissolved or dispersed liquid. 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 the wax is dissolved or dispersed as the mold release agent, an organic solvent that does not dissolve the wax 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.

(Dispersion of modified layered inorganic minerals)
The modified layered inorganic mineral can be mixed in the binder resin solution or dispersion.
Alternatively, the modified layered inorganic mineral and the binder resin may be mixed, melted and kneaded, and then pulverized to be used as a kneaded composite (master batch) of the modified layered inorganic mineral and the binder resin.

(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. 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 (methyl cellosolve, 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 forming the organic resin fine particles, any resin can be used as long as it can form an aqueous dispersion, 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. Two or more of these resins may be used in combination. 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 in 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 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 then 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 from the charged surface of the toner to be removed by washing.

(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 number of rotations is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. As temperature at the time of dispersion | distribution, it is 0-150 degreeC (under pressure) normally, Preferably it is 20-80 degreeC.

(Solvent removal)
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 adding a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with it, the toner composition is added to an aqueous medium. Before dispersing, 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 of 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
It is 0-150 degreeC, Preferably it is 20-98 degreeC. 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 particles such as the charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying 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 remodeled to lower the pulverization air pressure. Examples thereof include a device, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

<Charging imparting member>
In consideration of toner adhesion, the charge imparting member for recharging the toner remaining on the surface of the electrostatic latent image holding member after transfer from the electrostatic latent image bearing member to the next step is adhered due to charge-up if it is insulative. In order to generate, it is preferable that it is electroconductivity. The surface resistance is preferably 10 ^{2 to} 8 Ω / sq, and the volume resistance is preferably 10 ^{1 to} 6 Ω / sq.
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 electricity 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 the contact pressure with the electrostatic latent image carrier.
When 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 kv 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.

<Process cartridge>
In the image forming apparatus, it is desirable to configure a process cartridge as shown in FIG. 1 and replace the entire process cartridge during maintenance.
This is because the positioning of the image carrier and other members, such as the cleaning blade, is very important, and even if the positioning is slightly shifted, the intended cleaning performance may not be obtained, or the cleaning performance may differ between the left and right. This is because not only the service life may be shortened but also other members are easily contaminated.
In FIG. 1, 1 is an electrostatic latent image carrier, 2 is a transfer medium, 3 is a charging unit, 5 is an electrostatic latent image charging unit, 6 is a developing unit, and 7 is a transfer unit.

<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, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, further add 2 to 20 mg of the measurement sample as a solid content. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained.
The channel is, 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 having a particle size of 2.00 μm to less than 40.30 μm can be targeted.

(Average circularity)
As a shape measuring method, 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 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 is the average circularity.
This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been 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. .

(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 at 150 ° C. for 10 minutes, let stand at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, and again heat 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-based 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).

(Ratio of the area occupied by the modified layered inorganic mineral)
The ratio of the area occupied by the modified layered inorganic mineral in the region of 50 nm from the peripheral edge of the toner can be measured by FESEM (Field Emission Scanning Electron Microscope).

1. Sample preparation method The toner is embedded in an epoxy resin of several tens wt%. After curing, the sample was cut with a microtome using a diamond knife, the cross-section was taken out, and the reflected electron image of the sample obtained by fixing to a smooth metal plate with FESEM was observed.
The measurement conditions are as follows.
Equipment: ULTRA-55 manufactured by Carl Zeiss
Magnification: 1.3
Accelerating voltage 0.8 kV:
Irradiation current: 160 μA
The reflected electron image of the obtained sample was introduced into image analysis software (for example, Photoshop C2 manufactured by Adobe Systems). The layered inorganic mineral and the background of the image obtained by binarization were separated, and the area (A) of the layered inorganic mineral was determined. Further, the area (B) of the 50 nm region from the toner peripheral edge was determined, and the occupied area% of the layered inorganic mineral was determined from the following relational expression.
A ÷ B × 100 (%)

<Evaluation method>
(Evaluation of adhesion on development regulating blade)
The externally added toner (developer) was placed in a black toner cartridge of Epson LP-1500C, and the fixation on the development regulating blade at the initial stage (50 sheets) and after 800 sheets of blank paper was visually observed.
Evaluation level: ○ No sticking, △ Slightly sticking but no development unevenness, x sticking noticeable (soil stain evaluation)
The toner (developer) that has been externally added in the same manner as described above is put into a black toner cartridge of Epson LP-1500C, and a colorless transparent tape is pasted on the uncleaned portion after initial (50 sheets) and 800 sheets of blank paper. The scumming toner on the body was peeled off and a white paper was pasted, and then L * was measured with a spectral densitometer Xrite 939.

○: 90 or more Δ: 80 or more and less than 90 ×: less than 80

  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) 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 in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe 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 condenser, 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, 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 pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of master batch>
Carbon black (Regal 400R manufactured by Cabot Corporation): 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)>
In a container equipped with a stir bar and a thermometer, 378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9), release agent (WAX) dispersant (styrene-polyethylene polymer: Tg 73 ° C., number average molecular weight 7100) 96 parts (Releasing agent ratio 80%), 1450 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then 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, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. It was adjusted by adding ethyl acetate 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 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether 80 parts of a 48.5% aqueous solution of sodium 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 as [Aqueous Phase 1].

<Emulsification process>
[Pigment / WAX Dispersion 1] 967 parts, 2% by mass of Kraton APA (manufactured by Southern Clay Products) (converted to toner solids), 6 parts of isophorone diamine as amines, TK homomixer (manufactured by Special Machine) After mixing for 1 minute at 5,000 rpm, add 137 parts of [Prepolymer 1] and mix for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), then add 1200 parts of [Aqueous Phase 1]. 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].

<Washing->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 liquid 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 having a mesh size 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, the average circularity was 0.973, and the ATR value was 0.04. . Next, 1.5 parts of hydrophobic silica H2000 / 4 (particle size: 12 nm, manufactured by Clariant) and 0.5 part of hydrophobic silica RX50 (particle size: 40 nm, manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts of the base toner. To obtain [Toner 1] of the present invention.
The evaluation results for this toner 1 are shown in Table 1.

[Examples 2-6, Comparative Examples 1-3]
In Examples 2 to 6 and Comparative Examples 1 to 3, the amount of MON-7 and organic resin fine particle dispersion in preparation of the aqueous phase of Example 1 and the emulsification time during emulsification were changed as shown in Table 1. Except for this, the same procedure as in Example 1 was performed. The evaluation results for these toners are shown in Table 1.

  The toner of the present invention is excellent in chargeability, environmental stability, and durability stability, and gives a good printed matter that does not cause scumming or sticking. Therefore, an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. Can be suitably used as a developer for developing the toner.

Schematic diagram showing a process cartridge of the present invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrostatic latent image carrier 2 Transfer medium 3 Charging provision part 5 Electrostatic latent image charging means 6 Developing means 7 Transfer means

Claims (24)

  In a toner composed of a modified layered inorganic mineral obtained by modifying at least a part of ions between layers of a colorant, a binder resin, a release agent, and a layered inorganic mineral with organic ions, the volume average particle diameter is 4 to 8 μm. In the reflected electron image by thermal FE SEM of the toner cross section, the ratio of the area occupied by the modified layered inorganic mineral in the region 50 nm from the peripheral edge of the toner is 70% or more.   The toner according to claim 1, wherein the modified layered inorganic mineral is a modified layered inorganic mineral obtained by modifying at least a part of cations between layers of the layered inorganic mineral with an organic cation.   The toner is obtained by dispersing and / or emulsifying, in an aqueous medium, an oil phase which is a solution and / or a dispersion obtained by dissolving and / or dispersing a toner composition containing at least a binder resin and / or a binder resin precursor. The toner according to claim 1, wherein the toner is obtained by granulating the toner.   In the solution or dispersion, 0.05 to 2% by mass of a layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions is contained in the solid content of the solution or dispersion. The toner according to claim 3.   The toner according to claim 1, wherein the toner is obtained by removing an organic solvent after forming particles in an aqueous medium.   The toner according to any one of claims 1 to 5, wherein the toner is obtained by subjecting the toner to a washing treatment with a washing aqueous medium after the formation of particles in the aqueous medium and then a drying treatment.   The toner according to claim 1, wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher.   The toner according to claim 1, wherein the binder resin contains a polyester resin extended by urethane or / and urea bonds.   The toner according to claim 8, wherein the polyester resin described above contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines.   The toner according to claim 1, wherein the toner has a circularity of 0.95 or more and less than 0.99.   The said mold release agent contains 1 type single or 2 types or more selected from the group which consists of paraffins, synthetic esters, polyolefins, carnauba wax, and rice wax, Any one of Claims 1-10 characterized by the above-mentioned. Toner according to.   The toner according to claim 1, wherein the toner contains a charge control agent.   The toner according to claim 1, wherein the toner is a non-magnetic one-component developing toner.   An image forming apparatus using the non-magnetic one-component developing toner according to claim 13.   The image forming apparatus according to claim 14, wherein the image forming apparatus forms a multicolor image.   The image forming apparatus according to claim 14, wherein the image forming apparatus includes an endless intermediate transfer unit.   17. The image forming apparatus according to claim 14, wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photosensitive member and / or the intermediate transfer unit.   The image forming apparatus according to claim 14, wherein the image forming apparatus includes a blade cleaning unit.   The image forming apparatus according to claim 14, wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device.   The image forming apparatus according to claim 14, wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device.   The image forming apparatus according to claim 14, wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to the fixing member.   A toner container filled with the toner according to claim 1.   A toner container filled with the non-magnetic one-component developing toner according to claim 13.   In a process cartridge that integrally supports a developing unit and at least one unit selected from the group consisting of an image carrier, a charging unit, and a cleaning unit, and is detachable from the image forming apparatus main body, the developing unit includes: A process cartridge which holds toner and is the toner according to claim 1.

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