JP4966058B2 - Non-magnetic toner, image forming apparatus and process cartridge - Google Patents

Description

  The present invention relates to a non-magnetic toner, an image forming apparatus, and a process cartridge.

  Conventionally, a contact heating fixing method such as a heat roll fixing method has been widely adopted as a toner fixing method. A fixing device used for a heat roll fixing method includes a heating roll and a pressure roll, and passes a recording sheet carrying a toner image through a pressure contact portion (nip portion) between the heating roll and the pressure roll. As a result, the toner image is melted and fixed on the recording sheet.

  In the contact heating fixing method typified by the heat roll fixing method, the toner image on the recording sheet is fixed by bringing the surface of a heating member (for example, a heating roll) of the contact heating fixing device into contact with the toner image. It is necessary to prevent an offset phenomenon in which a part of the toner adheres to the next recording sheet and becomes dirty.

  In order to prevent the offset phenomenon, a technology for applying or impregnating fixing oil such as silicone oil to the heating roll or pressure roll of the fixing device is known, but fixing is performed from the viewpoint of downsizing and cost reduction of the fixing device. Oilless fixing devices that omit the oil application mechanism and fixing devices of a type that reduce the amount of fixing oil applied are employed. When such a fixing device is employed, a release agent is added to the toner as an anti-offset agent.

  In the case of the heat fixing method, the heating temperature is preferably as low as possible for energy saving. However, if the thermal properties of the binder resin constituting the toner are designed too low to achieve this, heat-resistant storage is possible. The property deteriorates and problems such as blocking occur. In order to achieve both, it is advantageous to use a polyester resin as the binder resin. Polyester resins have low viscosity and high elasticity compared to vinyl copolymer resins, so they have excellent low-temperature fixability and good heat-resistant storage properties.

  However, when a toner with a sufficient amount of release agent added to prevent offset is produced by a conventional pulverization method, a large amount of the release agent is exposed on the surface of the toner, causing problems such as filming and blocking. . On the other hand, a so-called polymerization method such as a suspension polymerization method in which a polymerization-reactive monomer is polymerized in an aqueous medium (see Patent Document 1) or an emulsion aggregation method in which fine particles are prepared and aggregated in advance by emulsion polymerization (see Patent Document 2). It is possible to relatively encapsulate a sufficient amount of the release agent, but since the suspension polymerization method and the emulsion aggregation method perform polymerization in an aqueous medium, generally vinyl copolymer resins are used. It is difficult to use a polyester resin that is polymerized at a high temperature of about 200 ° C. or higher.

  As a method for granulating toner using a polyester resin, a so-called dissolution suspension method is known in which a resin polymerized in advance is dissolved in an organic solvent and granulated in an aqueous medium. In this method, the molecular weight of the resin at the time of preparation becomes the molecular weight of the toner as it is, and in order to adjust the thermal characteristics of the toner, it is common to use a mixture of a low molecular weight resin and a high molecular weight resin. When the above resin is added, there is a problem that the viscosity of the solution becomes too high and the granulation property deteriorates, and many high molecular weight resins cannot be used. Therefore, the molecular weight of the low molecular weight resin must be increased, which is disadvantageous for low-temperature fixing.

  Therefore, there is a method in which a modified polyester having a reactive functional group is used instead of the high molecular weight resin, and the molecular weight is adjusted by elongation and / or crosslinking reaction after granulation. When this method is used, it is possible to adjust the thermal characteristics of the toner, but there is a problem that the structure of the toner is not sufficiently controlled, and the colorant, the release agent and the like are easily exposed on the surface. When the colorant is exposed on the surface, the charging performance of the toner changes. In particular, the narrower the particle size distribution, the more prominent the effect. Further, the larger the amount of the release agent exposed on the surface, the more advantageous the fixing property, but problems occur in developing durability, member contamination such as filming, and thermal stability. This is particularly noticeable when a low-viscosity release agent is used. For example, the influence of oxidation or the like also affects the dispersibility and chargeability.

On the other hand, when silicon oxide (SiO 2) or the like is used as the main component of the external additive, it is known that the chargeability of the toner changes by being embedded in the toner surface.
Japanese Patent No. 3195362 JP 2002-116574 A

  The present invention provides a non-magnetic toner that is excellent in fixability and chargeability and that can suppress the occurrence of background stains, and an image forming apparatus and a process cartridge using the non-magnetic toner in view of the above-described problems of the prior art. The purpose is to do.

  The invention according to claim 1 is a non-magnetic toner having toner base particles containing at least a colorant and a binder resin, and an external additive, wherein the surface of the toner base particles is a resin having at least a silanol group. And the external additive contains at least particles made of silicon oxide.

  According to a second aspect of the present invention, in the nonmagnetic toner according to the first aspect, the surface of the toner base particles is formed by agglomerating and / or fusing the particles containing the resin having at least a silanol group. It is formed.

  According to a third aspect of the present invention, in the nonmagnetic toner according to the first or second aspect, the base particles of the toner include a core material portion containing at least a colorant and a first binder resin, and the core material A shell material part made of a second binder resin covering the part, wherein the second binder resin contains at least the resin having at least a silanol group.

  According to a fourth aspect of the present invention, in the nonmagnetic toner according to any one of the first to third aspects, the silanol group has a general formula.

R1, R2 and R3 are each independently a branched or linear alkyl group having 1 to 6 carbon atoms and 3 or more carbon atoms. It is a hydrocarbon group selected from the group consisting of 6 or less alicyclic groups and a substituted or unsubstituted phenyl group.

  According to a fifth aspect of the present invention, in the nonmagnetic toner according to any one of the first to fourth aspects, the shell material portion has a thickness of 20 nm or more and 300 nm or less, and a volume average particle size of 4 μm or more. In addition to being 10 μm or less, the average circularity is 0.910 or more and 0.990 or less.

  The invention according to claim 6 is the nonmagnetic toner according to any one of claims 3 to 5, wherein the first binder resin is a polyester resin having a glass transition temperature of 40 ° C. or more and 80 ° C. or less. It is characterized by containing.

  According to a seventh aspect of the invention, in the nonmagnetic toner according to any one of the third to sixth aspects, the first binder resin contains a modified polyester resin.

  The invention according to claim 8 is the nonmagnetic toner according to claim 7, wherein the modified polyester resin has a urethane group and / or a urea group.

  The invention according to claim 9 is the nonmagnetic toner according to any one of claims 3 to 8, wherein the first binder resin reacts a polyester resin having an isocyanate group at the terminal with amines. It contains the resin obtained by this.

  10. The non-magnetic toner according to claim 1, wherein the toner base particles preferably have a surface tension of 30 mN / m or more and 60 mN / m or less.

  A tenth aspect of the present invention is the nonmagnetic toner according to any one of the first to ninth aspects, wherein the toner base particles are granulated using an organic solvent in at least an aqueous medium. It is obtained by removing the organic solvent later.

  According to an eleventh aspect of the present invention, in the nonmagnetic toner according to any one of the first to tenth aspects, the base particle of the toner is at least granulated in an aqueous medium, and then an aqueous medium is used. It is obtained by washing and drying.

  According to a twelfth aspect of the present invention, the nonmagnetic toner according to any one of the first to eleventh aspects further includes a release agent.

  A thirteenth aspect of the present invention is the nonmagnetic toner according to any one of the first to twelfth aspects, further comprising a charge control agent.

  According to a fourteenth aspect of the present invention, the non-magnetic toner according to any one of the first to thirteenth aspects is used in a one-component development system.

  According to a fifteenth aspect of the present invention, in the image forming apparatus, an image is formed using the nonmagnetic toner according to any one of the first to fourteenth aspects.

  According to a sixteenth aspect of the present invention, in the image forming apparatus according to the fifteenth aspect, a multicolor image is formed.

  According to a seventeenth aspect of the present invention, in the image forming apparatus according to the fifteenth or sixteenth aspect, the image forming apparatus includes an endless intermediate transfer unit.

  According to an eighteenth aspect of the present invention, in the image forming apparatus according to any one of the fifteenth to seventeenth aspects, a photosensitive member and a cleaning unit that cleans toner remaining on the photosensitive member and / or the intermediate transfer unit. The cleaning means does not have a cleaning blade.

  According to a nineteenth aspect of the present invention, in the image forming apparatus according to any one of the fifteenth to seventeenth aspects, a photosensitive member and a cleaning unit that cleans toner remaining on the photosensitive member and / or the intermediate transfer unit. The cleaning means has a cleaning blade.

  According to a twentieth aspect of the present invention, in the image forming apparatus according to any one of the fifteenth to nineteenth aspects, the image forming apparatus further includes a fixing unit that fixes an image using a roller having a heating device.

  According to a twenty-first aspect of the present invention, in the image forming apparatus according to any one of the fifteenth to twentieth aspects, the image forming apparatus includes a fixing unit that fixes an image using a belt having a heating device.

  According to a twenty-second aspect of the present invention, in the image forming apparatus according to any one of the fifteenth to twenty-first aspects, the fixing member includes a fixing unit that does not require oil application.

  According to a twenty-third aspect of the present invention, in the process cartridge, the photosensitive member and the electrostatic latent image formed on the photosensitive member are developed using the non-magnetic toner according to any one of the first to fourteenth aspects. The developing means is at least integrally supported and detachable from the main body of the image forming apparatus.

  According to the present invention, it is possible to provide a nonmagnetic toner that is excellent in fixability and chargeability and can suppress the occurrence of background stains, and an image forming apparatus and a process cartridge using the nonmagnetic toner.

  Next, the best mode for carrying out the present invention will be described.

  The non-magnetic toner of the present invention (hereinafter referred to as toner) has toner base particles containing at least a colorant and a binder resin and an external additive, and the surface of the toner base particles has at least a silanol group. The resin contains at least a resin, and the external additive contains at least particles made of silicon oxide.

When silicon oxide (SiO ₂ ) or the like is used as the main component of the external additive, it is known that the chargeability of the toner changes as it is buried in the surface of the toner. This is considered that the contribution rate of the charging property of the toner base particles becomes high and converges gradually. These effects increase as the charging properties of the base particles and the toner after external addition differ, and in particular, the degree of influence of the relationship between the materials and properties constituting the surface of the base particles and the external additives on the charging characteristics. It is thought that it is large. Furthermore, when the toner that has not deteriorated and the deteriorated toner are mixed, the distribution of the charge amount tends to be wide.

  As a result of diligent research on the relationship between the surface of the toner base particles and the external additive, the surface of the toner base particles is a resin having a silanol group similar to silicon oxide used for the external additive. It has been found that the change in charging property accompanying the change in the adhesion state of the external additive is remarkably improved by containing at least. At this time, it is more preferable that the difference in chargeability between the base particles and the toner after external addition is small.

  In the present invention, the toner base particles have a core part containing at least a colorant and a binder resin (A) and a shell part made of the binder resin (B) covering the core part. The dressing resin (B) preferably contains at least a resin having a silanol group. As a result, it is possible to narrow the distribution of the charge amount of the toner base particles caused by the colorant and the release agent, which is remarkable in multicolor development, etc., and as a means for functional separation of toner characteristics by structure control Increases nature. Furthermore, by using the shell portion that suppresses the difference in chargeability from the external additive, it is possible to suppress the change in the chargeability of the toner with time and to form a stable image.

  Silanol groups are usually obtained by chemically treating alkoxysilyl groups.

Wherein R1, R2 and R3 are each independently selected from the group consisting of C1-C6 branched or straight chain alkyl groups and C3-C6 alicyclic groups and substituted or unsubstituted phenyl groups. It is preferably obtained by chemically treating the functional group represented by

  The resin having at least a silanol group is not particularly limited, but in order to coat the surface of the toner base particles, the glass transition temperature is usually 40 to 80 ° C., preferably 45 to 70 ° C.

  In the present invention, the toner base particles are preferably granulated in an aqueous medium because silanol groups are likely to be present in the vicinity of the surface.

  In this invention, it is preferable that the film thickness of a shell material part is 20-300 nm, More preferably, it is 20-250 nm, Most preferably, it is 30-200 nm. If the thickness of the shell portion is less than 10 nm, the influence on the charging property of the colorant may not be sufficiently mitigated. In addition, the charging property may be easily changed by embedding the external additive. On the other hand, when the film thickness of the shell material part exceeds 300 nm, the release of the release agent becomes insufficient, and the fixability (separability, strength) may be lowered.

  The toner preferably has a volume average particle diameter of 4 to 10 μm. If the volume average particle size is smaller than 4 μm, each process of image formation may be hindered, and if it is larger than 10 μm, the resolution of the image may be lowered.

  Further, the toner preferably has an average circularity of 0.910 to 0.990, more preferably 0.930 to 0.990, and particularly preferably 0.950 to 0.990. If the average circularity is less than 0.910, the toner charge distribution is likely to vary, and transfer efficiency and dot reproducibility may be reduced. If it is lowered, it may be difficult to hold on the carrier, which may easily cause scumming or poor conveyance.If a cleaning system is installed, untransferred toner may be left behind. May be easier.

  In the present invention, the toner base particles preferably have a surface tension of 30 to 60 mN / m. If the surface tension is less than 30 mN / m, the amount of silanol groups introduced may be insufficient, and the polarity of the surface may be reduced. If the surface tension is greater than 60 mN / m, the affinity with water is too high and the humidity is high. In some cases, it may be difficult to ensure chargeability.

  In the present invention, as the binder resin (A), styrene such as polystyrene, poly (p-chlorostyrene), polyvinyltoluene and the like, and polymers of the substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Styrene-vinyl methyl ketone copolymer, styrene Styrene copolymers such as tadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester resin, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or Examples thereof include alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins and paraffin waxes, and these can be used alone or in combination. Among these, a polyester resin is preferable.

  In the present invention, the polyester resin is not particularly limited and any polyester resin can be used, and several polyester resins may be mixed and used. Examples of the polyester resin include polycondensates of the following polyol (1) and polycarboxylic acid (2).

  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 and 3,3′-difluoro-4,4′-dihydroxybiphenyl; bis (3-fluoro-4-hydroxyphenyl) Tan, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5- Bis (hydroxyphenyl) such as difluoro-4-hydroxyphenyl) propane (also known as tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane ) Alkanes; Bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols Alkylene oxides of the above bisphenols (ethylene oxide, propylene Oxides, butylene oxides, etc.), etc. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide additions of bisphenols, and particularly preferred are additions of alkylene oxides of bisphenols. And a combination of this and an alkylene glycol having 2 to 12 carbon atoms.

  Further, as the trivalent or higher polyol (1), a trivalent or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (trisphenol PA) , Phenol novolac, cresol novolac, etc.); alkylene oxide adducts of the above-mentioned trihydric or higher polyphenols.

  In addition, the said polyol can be individual or can use 2 or more types together, and is not limited above.

  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′-bifu Nildicarboxylic 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.

  Furthermore, as polycarboxylic acids having 3 or more valences, aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), anhydrides of the above aromatic polycarboxylic acids, lower alkyl esters (methyl esters) , Ethyl ester, isopropyl ester, etc.).

  In addition, the said polycarboxylic acid can be used individually or in combination of 2 or more types, It is not limited to the above.

Regarding the ratio of the polyol (1) and the polycarboxylic acid (2) when synthesizing the polyester resin, the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH] is used.
However, it is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

  The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When the peak molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 10,000, the low-temperature fixability may be lowered.

  In this invention, it is preferable that binder resin (A) contains the polyester resin whose glass transition temperature is 40 degreeC or more and 80 degrees C or less. When the glass transition temperature is less than 40 ° C, the heat-resistant storage stability may be lowered, and when it exceeds 80 ° C, the low-temperature fixability may be lowered.

  In the present invention, the binder resin (A) preferably contains a modified polyester resin for adjusting viscoelasticity for the purpose of preventing offset, and more preferably a modified polyester having a urethane group and / or a urea group. Contains resin.

  The content of the modified polyester resin in the binder resin (A) is preferably 20% by weight or less, more preferably 15% by weight or less, and particularly preferably 10% by weight or less. When the content of the modified polyester resin is more than 20% by weight, the low-temperature fixability may be lowered. The modified polyester resin may be directly mixed or may form toner base particles, but from the viewpoint of manufacturability, a polyester resin having an isocyanate group at the terminal (hereinafter referred to as prepolymer (A)), It is preferable to obtain a modified polyester resin by mixing reactive amines and performing an extension reaction and / or a crosslinking reaction during or after granulation.

  The prepolymer (A) is a polycondensate of polyol (1) and polycarboxylic acid (2), and can be obtained by further reacting a polyester resin having an active hydrogen group with polyisocyanate (3). Examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like, and an alcoholic hydroxyl group is preferable.

  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, phenol derivatives, oximes, caprolactams, etc. It may be blocked. In addition, these can use 2 or more types together.

  Regarding the ratio of the polyisocyanate (3) and the polyester resin having an active hydrogen group when synthesizing the prepolymer (A), the equivalent ratio [NCO] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester resin having a hydroxyl group is used. ] / [OH] is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. When it is less than 1, the content of urethane groups and / or urea groups in the modified polyester resin is decreased, and offset resistance is reduced. May decrease.

  The content of the component derived from polyisocyanate (3) in the prepolymer (A) is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. When the content is less than 0.5% by weight, the offset resistance may be lowered, and when it exceeds 40% by weight, the low-temperature fixability may be lowered.

  The number of isocyanate groups per molecule of the prepolymer (A) is usually 1 or more, preferably 1.5 to 3, more preferably 1.8 to 2.5. When the number of isocyanate groups is less than 1, the molecular weight of the modified polyester resin is lowered, and offset resistance may be lowered.

  In the present invention, amines (B) can be used as an extender and / or a crosslinking agent. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), amino group blocked B1 to B5 (B6) Etc.

  Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); alicyclic diamines ( 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc .; aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylene) Amine) and the like.

  Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetraamine.

  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 B1 to B5 (B6) in which an amino group is blocked include B1 to B5 and ketimine compounds and oxazoline compounds obtained from ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

  Furthermore, a terminator can be used in the extension reaction and / or the cross-linking reaction as necessary, and the molecular weight of the modified polyester resin can be adjusted. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking these (ketimine compounds).

  The ratio of the prepolymer (A) to the amines (B) when synthesizing the modified polyester resin is equivalent to the isocyanate group [NCO] of the prepolymer (A) and the amino group [NHx] of the amines (B). The ratio [NCO] / [NHx] 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 modified polyester resin is decreased, and the hot offset resistance may be decreased.

  In the present invention, as the colorant, 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, Physe Red, p-chloro-o 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 vermilion, 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 in the toner is usually 1 to 15% by weight, preferably 3 to 10% by weight.

  In the present invention, the colorant can also be used as a master batch combined with a resin. As the resin to be kneaded together with the production of the master batch or the master batch, the same resin as the binder resin (A) can be used.

  The master batch can be obtained by mixing and kneading a resin and a colorant under a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method, which is a method of mixing and kneading an aqueous paste of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and the organic solvent, uses the wet cake of the colorant as it is. Therefore, it is not necessary to dry and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

  The toner of the present invention preferably further contains a release agent. As the release agent, known ones can be used, and examples thereof include polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); ); Dialkyl ketones (distearyl ketone and the like) and the like. Among the carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

  In the present invention, the content of the release agent in the toner is preferably 5 to 15% by weight. If the content of the release agent is less than 5% by weight, there is a possibility that the margin for preventing offset may be lost. If the content exceeds 15% by weight, the release agent melts at a low temperature. The release agent oozes out from the inside of the toner during stirring in the developing unit and adheres to the toner regulating member and the photoconductor, and image noise may occur.

  Moreover, it is preferable that melting | fusing point measured by the differential scanning calorimeter (DSC) of a mold release agent is 65-115 degreeC. When the melting point is lower than 65 ° C., the fluidity may be lowered. When the melting point is higher than 115 ° C., the low-temperature fixability may be lowered.

  The toner of the present invention preferably further contains a charge control agent. Known charge control agents 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, fluorosurfactants, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E- of salicylic acid metal complex 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (made of Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Japan Carlit ), Copper phthalocyanine, perylene, quinacridone, a Zeo pigment, and other polymer compounds having a sulfonic acid group, a carboxyl group, a quaternary ammonium salt, and the like.

  In the present invention, the external additive for assisting the fluidity, developability and chargeability of the toner base particles contains at least particles composed of silicon oxide, but other inorganic particles can also be used. As the inorganic particles, small-sized particles used as a fluidizing agent having an average primary particle size of 7 to 40 nm, medium-sized particles having a spacer effect that can be sufficiently adhered (fixed) to toner having an average primary particle size of 40 to 150 nm In addition, there may be mentioned large-sized particles used as a charging or cleaner auxiliary agent having an average primary particle size of 200 nm or more (particularly 0.25 to 2 μm). Since the small and medium diameter particles have a large influence on the embedding, the average primary particle diameter is preferably equal to or less than the thickness of the shell material layer, and more preferably 2/3 of the thickness of the shell material layer. Hereinafter, it is particularly preferably 1/2 or less of the thickness of the shell material layer. The large-diameter particles are not particularly restricted because they tend to adhere to or leave the toner base particles and have little influence on embedding.

  The average primary particle size of the inorganic particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m <2> / g.

  The content of inorganic particles in the toner is preferably 0.01 to 5% by weight, more preferably 0.01 to 2.0% by weight. Examples of inorganic particles other than silicon oxide include alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Examples of the external additive include polymer particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, copolymers of methacrylic acid ester and acrylic acid ester, silicone resin, benzoguanamine, nylon, and the like. And particles such as polycondensation resins and thermosetting resins.

  Such external additives can be surface treated to increase hydrophobicity, thereby suppressing a decrease in flow characteristics and charging characteristics even under high humidity. Examples of the surface treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Can be mentioned.

  In order to make it easier to remove the toner after transfer remaining on the photoreceptor and the primary transfer medium, a cleaning property improving agent can be added as an external additive. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymer particles produced by soap-free emulsion polymerization such as polymethyl methacrylate particles, polystyrene particles, and the like. The polymer particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  In the present invention, it is preferable that the surface of the toner base is uniformly coated on the surface of the toner base with a resin having a functional group represented by the chemical structural formula (1). For example, the shell material portion can be formed by adjusting the polarity, molecular weight, etc. of the resin within a range that does not impair the compatibility, and by orienting the resin on the surface or aggregating and / or fusing the particles. As a result, the surface property and charge amount distribution of the toner particles become uniform, so that the mobility of the toner can be improved or stabilized.

  In the present invention, the resin having a functional group represented by the chemical structural formula (1) is preferably a vinyl copolymer resin. Any vinyl-based copolymer resin can be used without particular limitation as long as it has a functional group represented by the chemical structural formula (1), and several types of vinyl-based copolymer resins may be mixed. May be used. The weight average molecular weight is preferably 50000 or less, and more preferably 30000 or less. When the weight average molecular weight is more than 50,000, the low-temperature fixability may be lowered. The glass transition temperature is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. When the glass transition temperature is higher than 80 ° C., the low-temperature fixability may be lowered, and when it is lower than 40 ° C., the heat-resistant storage property may be lowered.

The vinyl copolymer resin is obtained by copolymerizing a vinyl monomer, and the vinyl monomers having no functional group represented by the chemical structural formula (1) include the following (1) to (10). Can be mentioned.
(1) Vinyl hydrocarbons As aliphatic vinyl hydrocarbons, alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc.), Examples include alkadienes (butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.).

  Examples of alicyclic vinyl hydrocarbons include mono- or dicycloalkenes and alkadienes (cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc.) and terpenes (pinene, limonene, indene, etc.). It is done.

As aromatic vinyl hydrocarbons, styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene) Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc.) and vinyl naphthalene.
(2) Carboxyl group-containing vinyl monomers and salts thereof As carboxyl group-containing vinyl monomers, unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyls thereof (having 1 to 24 carbon atoms) ) Esters ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, monoalkyl itaconic acid, glycol itaconic ether, citraconic acid, citraconic acid Monoalkyl, cinnamic acid, etc.).
(3) Sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof As sulfonic acid group-containing vinyl monomers, alkene sulfonic acids having 2 to 14 carbon atoms (vinyl sulfonic acid, (meth) allyl sulfonic acid) , Methyl vinyl sulfonic acid, styrene sulfonic acid etc.) and alkyl derivatives thereof having 2 to 24 carbon atoms (α-methyl styrene sulfonic acid etc.); sulfo (hydroxy) alkyl (meth) acrylate or (meth) acrylamide (sulfopropyl (meth) ) Acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meta ) Acrylyloxy-2-hydroxypropanesulfo Acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamido-2-hydroxypropane sulfonic acid, alkyl allyl sulfosuccinic acid) and the like (the number of 3 to 18 carbon atoms) are exemplified.

Examples of vinyl sulfate monoesters include polyoxyalkylene (ethylene, propylene, butylene) (n = 2 to 30; may be single, random or block) mono (meth) acrylate sulfate (polyoxypropylene (n = 5 to 5). 15) Monomethacrylate sulfate and the like.
(4) Phosphoric acid group-containing vinyl monomers and salts thereof As phosphoric acid group-containing vinyl monomers, (meth) acryloyloxyalkyl phosphoric acid monoester (2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxy) Ethyl phosphate etc.); (meth) acryloyloxyalkyl (C1-C24) phosphonic acids (2-acryloyloxyethylphosphonic acid etc.).

Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, 4 A class ammonium salt is mentioned.
(5) Hydroxyl group-containing vinyl monomer As the hydroxyl group-containing vinyl monomer, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate , (Meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl Examples include ether and sucrose allyl ether.
(6) Nitrogen-containing vinyl monomers As amino group-containing vinyl monomers, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (Meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N- Vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole and These salts and the like.

  Examples of amide group-containing vinyl monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, and N, N-methylene-bis (meth) acrylamide. Cinnamic acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.

  Examples of the nitrile group-containing vinyl monomer include (meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.

  Quaternary ammonium salt-containing vinyl monomers include tertiary amine group-containing vinyls such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, and diallylamine. And quaternized products of monomer based on quaternization using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate.

Nitrostyrene etc. are mentioned as a nitro group containing vinyl-type monomer.
(7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomer include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and p-vinylphenylphenyl oxide.
(8) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone As vinyl ester, vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate , Cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate; alkyl (meth) acrylate having 1 to 50 carbon atoms (methyl (meth) acrylate, ethyl (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acryl , Hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.); dialkyl fumarate (two alkyl groups are linear, branched or alicyclic having 2 to 8 carbon atoms) Dialkyl maleates (two alkyl groups are straight, branched or alicyclic alkyl groups having 2 to 8 carbon atoms); poly (meth) allyloxyalkanes (Diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.); vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) Mono (meth) acrylate, polypropylene glycol (molecular weight 500 Monoacrylate, (meth) acrylic acid ester of 10 mol adduct of methyl alcohol ethylene oxide, (meth) acrylic acid ester of 30 mol adduct of lauryl alcohol ethylene oxide, etc.); (meth) acrylic acid ester of polyhydric alcohols (ethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.).

  Examples of vinyl (thio) ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, 2-ethylhexyl vinyl ether, vinyl phenyl ether, 2-methoxyethyl vinyl ether, methoxy butadiene, 2-butoxyethyl vinyl ether, 3,4 -Dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, 2-ethylmercaptoethyl vinyl ether, acetoxystyrene, phenoxystyrene and the like.

  Examples of the vinyl ketone include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

Examples of the vinyl sulfone include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, and the like.
(9) Other vinyl monomers Examples of other vinyl monomers include isocyanate ethyl (meth) acrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate.
(10) Fluorine atom element-containing vinyl monomer As the fluorine atom element-containing vinyl monomer, 4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meta) ) Acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate Relate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate, the corresponding compound derived from α-fluoroacrylic acid, bis ( Hexafluoroisopropyl) itaconate, bis (hexafluoroisopropyl) maleate, bis (perfluorooctyl) itaconate, bis (perfluorooctyl) maleate, bis (triflu) Roechiru) itaconate, bis (trifluoroethyl) maleate, vinyl heptafluorobutyrate, vinyl perfluoro heptanoate, vinyl perfluoro nonanoate, vinyl perfluorooctanoate like.

  Examples of vinyl monomers having at least a silanol group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, and 3-methacryloyloxypropyltrimethoxy. Silane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldipropoxysilane, 3-methacryloyloxypropylmethyldiisopropoxysilane 3-methacryloyloxypropyldimethylcyclohexyloxysilane, p-styryldimethylphenoxysilane, p Steel Riruto Revenge oxy silane and the like, but not particularly limited thereto.

  The particles containing at least a vinyl copolymer resin having a silanol group are preferably used in a state of being dispersed in an aqueous medium. The particles containing such a vinyl copolymer resin can be produced by general emulsion polymerization or the like.

  The method for producing the toner of the present invention is not particularly limited, but is preferably produced by the following production method.

  The method for producing a toner of the present invention comprises a step of granulating a core material part by dispersing a solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a polyester resin and a colorant in an organic solvent in an aqueous medium. And at least a step of adding an aqueous dispersion in which particles containing a resin having a functional group represented by the chemical structural formula (1) are dispersed in an aqueous medium and attaching the particles to the core part. Is preferred. More specifically, it is as follows.

  The organic solvent that dissolves or disperses the toner composition is preferably volatile with a boiling point of less than 100 ° C., since it can be easily removed 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, Examples include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These 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 toner composition may be dissolved or dispersed at the same time, but is usually dissolved or dispersed independently, and the organic solvents used at that time may be different or the same, but considering the subsequent solvent treatment, Is preferred.

  The solution or dispersion of the toner composition preferably has a resin concentration of 40 to 80% by weight. When the resin concentration exceeds 80% by weight, it becomes difficult to dissolve or disperse and the viscosity becomes high and it is difficult to handle. On the other hand, if it is less than 40% by weight, the amount of toner produced is reduced. When mixing the polyester resin and the prepolymer, they may be mixed in the same solution or dispersion, or may be prepared separately, but considering the solubility and viscosity of each, separate dissolution Alternatively, it is preferable to prepare a dispersion.

  The colorant may be dissolved or dispersed alone, or may be mixed in a polyester resin solution or dispersion. If necessary, a dispersion aid or a polyester resin may be added, or a master batch may be used.

  When the wax is dissolved or dispersed as the release agent, or when an organic solvent in which the wax does not dissolve is used, 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, heating to the melting point of the wax, cooling with stirring, and then dispersing with a disperser such as a bead mill may shorten the dispersion time. Further, a plurality of waxes may be mixed and used, or a dispersion aid or a polyester resin may be added.

As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (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 weight of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. When the amount of the aqueous medium used is less than 50 parts by weight, the dispersion state of the toner composition may be deteriorated. When the amount exceeds 20000 parts by weight, it is preferable to disperse the inorganic dispersant or resin particles in advance in the aqueous medium when the toner composition solution or dispersion is dispersed in the uneconomic aqueous medium. Thereby, the particle size distribution can be narrowed and stably dispersed.

  As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

  Further, as the resin forming the resin 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, For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like can be mentioned. 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 preferred because an aqueous dispersion of fine spherical resin particles can be easily obtained.

Although the method of manufacturing the aqueous dispersion of resin particles is not particularly limited, the following (a) to (h) can be mentioned.
(A) In the case of a vinyl resin, an aqueous dispersion of resin particles is directly produced 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 a polyaddition or condensation resin such as a polyester resin, a polyurethane resin, and an epoxy resin, a precursor (monomer, oligomer, etc.) or a solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, After that, the resin particles are cured by heating or adding a curing agent to produce an aqueous dispersion of resin particles.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it is preferably a precursor (monomer, oligomer, etc.) or a solution thereof (liquid). ) After a suitable emulsifier is dissolved therein, water is added to carry out phase inversion emulsification.
(D) Resin produced in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) After pulverizing and classifying using a fine pulverizer, resin particles are obtained, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution 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 sprayed in the form of a mist. Thus, the resin particles are obtained and then dispersed in water in the presence of a suitable dispersant.
(F) 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. The resin particles are precipitated by adding a solvent or by cooling a resin solution previously dissolved in a solvent by heating, and after removing the solvent to obtain resin particles, in a water-based medium in the presence of an appropriate dispersant. Disperse.
(G) A resin solution 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 used as an appropriate dispersant. After the dispersion in an aqueous medium, the solvent is removed by heating, decompression or the like.
(H) An appropriate emulsifier is added to a resin solution prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.). After dissolving, water is added and phase inversion emulsified.

  In addition, a surfactant or the like may be used as necessary in order to emulsify and disperse the toner composition solution or dispersion in an aqueous medium. Surfactants include alkylbenzene sulfonate, α-olefin sulfonate, anionic surfactants such as phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyl Quaternary ammonium salt type cationic surfactants such as trimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol derivative, etc. Nonionic surfactants such as alanine, dodecyl bis (aminoethyl) glycine, bis (octylaminoethyl) glycine, and N-alkyl-N, N-dimethylammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkyl carboxylic acid having 2 to 10 carbon atoms and a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 to 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 salts, perfluoroalkyl carboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Further, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, etc. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. Polymeric protective colloids include acids (acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, etc.); (Meth) acrylic monomer (β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxy methacrylate) Propyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylol acetate Rilamide, N-methylol methacrylamide, etc.); vinyl alcohol or ethers with vinyl alcohol (vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.); esters of vinyl alcohol and compounds containing a carboxyl group (vinyl acetate, Vinyl propionate, vinyl butyrate, etc.); acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides (acrylic acid chloride, methacrylic acid chloride, etc.); those having a nitrogen atom or its heterocyclic ring ( Homopolymers or copolymers such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc .; polyoxyethylenes (polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxy) Propylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl ester, etc.); celluloses (methyl cellulose) , Hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) can be used.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble compound is used as the dispersion stabilizer, the calcium phosphate salt is dissolved with an acid such as hydrochloric acid and then washed with water, etc. Salt can be removed. In addition, it can be removed by an operation such as enzymatic degradation. When a dispersant is used, it can be used in a state where the dispersant remains on the surface of the core part, but it is preferable to remove it by washing from the charged surface of the toner.

  The dispersion method is not particularly limited, and known methods 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 average particle size of the dispersion 2 to 20 μm, a high-speed shearing method 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, and preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature at the time of dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually raising the temperature of the whole system under normal pressure or reduced pressure and evaporating and removing the organic solvent in the droplets can be employed. It is also possible to spray the emulsified dispersion in a dry atmosphere to remove the organic solvent in the droplets and to evaporate and remove the surfactant. As the dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like can be used, but various airflows heated to a temperature equal to or higher than the boiling point of the organic solvent are generally used. . At this time, the processing time can be shortened by using a spray dryer, a belt dryer, a rotary kiln or the like.

  Next, a process of attaching particles containing a resin having a functional group represented by the chemical structural formula (1) to the surface of the core member will be described. In this step, it is preferable to use an aqueous dispersion in which particles containing a resin having a functional group represented by the chemical structural formula (1) are dispersed. This dispersion can be produced by a usual emulsion polymerization method and may be used as it is. Further, for example, a surfactant or the like may be added to stabilize the dispersion of the core material part and the particles. The timing of introducing the particles may be before the organic solvent is removed or after the removal.

  In this step, the pH may be adjusted with sodium hydroxide, hydrochloric acid or the like in order to more efficiently attach the particles to the core member. Moreover, you may add 1-3 metal salt as a coagulant | flocculant. Examples of the monovalent metal constituting the salt include lithium, potassium, and sodium. Examples of the divalent metal include calcium and magnesium. Examples of the trivalent metal include aluminum. Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion and sulfate ion.

  Moreover, you may heat and accelerate | stimulate adhesion of particle | grains. However, when the particles are adhered at or near the glass transition temperature of the particles, aggregation and / or fusion between the particles hardly proceed, so that further heating further promotes aggregation and / or fusion. It is preferable to promote the coating of the core part and make the surface of the shell part uniform. At this time, the heating temperature and the heating time are appropriately adjusted from the viewpoint of adjusting the degree of surface uniformity and adjusting the sphericity as the toner base particles.

  The amines (B) may be mixed in an organic solvent before dispersing the toner composition in the aqueous medium, or may be added to the aqueous medium. The time required for the reaction for synthesizing the modified polyester is appropriately selected depending on the reactivity of the prepolymer (A) and the amines (B), but is usually 1 minute to 40 hours, preferably 1 to 24 hours. is there. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. This reaction may be performed before the step of attaching particles to the core member, or may be performed simultaneously during this step. Further, this process may be completed. In addition, a well-known catalyst can be used as needed.

  A known method is used in the step of washing and drying the toner base 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-exchanged water at room temperature to about 40 ° C., and if necessary, pH adjusted with acid or alkali, The process of solid-liquid separation is repeated several times. Thus, after removing impurities, surfactants, and the like, toner base particles are obtained by drying with an air dryer, circulation dryer, vacuum dryer, vibration fluid dryer, or the like. At this time, the fine particle component may be removed by centrifugation or the like, and after drying, a desired particle size distribution can be obtained using a known classifier as necessary.

  A means for mixing the external additive and the toner base particles is not particularly limited, and a mixer such as a Henschel mixer or a super mixer can be used. Also, by applying mechanical impact force to the mixed powder and fixing and fusing the external additive on the surface of the toner base particles, it is possible to suppress detachment of the external additive from the toner surface. it can. Specifically, a method of applying an impact force to the mixture with blades rotating at high speed, a method of accelerating the mixture in a high-speed air stream, accelerating the particles, or a method of causing the composite particles to collide with an appropriate collision plate, etc. be able to. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

  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.

  Next, a method for measuring the particle size distribution of the toner will be described. Examples of the toner particle size distribution measuring apparatus by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method will be described below. First, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic solution. Here, the electrolytic solution is prepared by preparing about 1 wt% NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added as a solid content. The electrolyte in which the sample is suspended is subjected to a dispersion process for 1 to 3 minutes with an ultrasonic disperser, and the volume and number distribution of the toner are measured with a measuring device using a 100 μm aperture to obtain a volume distribution and a number distribution. calculate. 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, 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm 6.35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Particles having a particle size of 2.00 μm or more and less than 40.30 μm can be used using 13 channels of 25.40 μm or more and less than 32.00 μm; 32.00 μm or more and less than 40.30 μm.

  As a method for measuring the shape of the toner, an optical detection band method is suitable in which a suspension containing toner 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. is there. 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. The average circularity can be measured by a flow type particle image analyzer FPIA-2000. As a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Add 0.1 to 0.5 g of the measurement sample. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for 1 to 3 minutes, and the concentration of the dispersion is measured at 3000 to 10,000 / μl.

  The molecular weight of a resin such as a polyester resin or a vinyl copolymer resin can be measured under the following conditions by normal GPC (gel permeation chromatography).

Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Sample concentration: 0.05 to 0.6% by weight
Sample injection volume: 0.01ml
The number average molecular weight and the weight average molecular weight can be calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample from the molecular weight distribution of the resin measured under the above conditions. As the monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 10 2 to 7.5 × 10 6 are used.

  The glass transition temperature of a resin such as polyester resin or vinyl copolymer resin is, for example, 150 using a differential scanning calorimeter DSC-6220R (manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min from room temperature. After heating to 150 ° C., let stand at 150 ° C. for 10 minutes, cool the sample to room temperature, let stand for 10 minutes, and again heat to 150 ° C. at a heating rate of 10 ° C./min. The height of the baseline above the glass transition temperature can be obtained from a curved portion corresponding to 1/2.

  The particle size of the resin particles and the like can be measured as a dispersion using a measuring device such as LA-920 (manufactured by Horiba, Ltd.), UPA-EX150 (manufactured by Nikkiso Co., Ltd.).

  A method for measuring the film thickness of the shell material will be described below. The toner is embedded in an epoxy resin, cut into ultrathin sections of about 100 nm, stained with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM) at a magnification of 5000 and 20000, and photographed. From this photograph, 10 samples equivalent to the volume average particle diameter of the toner are selected, and image evaluation is performed to obtain three film thicknesses of the shell material per sample, and the average of 10 samples is obtained.

  The process cartridge of the present invention at least integrally supports a photoconductor and a developing unit that develops the electrostatic latent image formed on the photoconductor using the toner of the present invention, and further appropriately selected as necessary. The charging unit, the transfer unit, the cleaning unit, the neutralizing unit, and the like may be integrally supported. The developing unit includes at least a developer carrying member that carries and conveys toner, and may further include a layer thickness regulating member for regulating the thickness of the toner layer to be carried.

  The process cartridge of the present invention can be detachably provided in the main body of an image forming apparatus such as various electrophotographic apparatuses, facsimile machines, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

  FIG. 1 shows an example of the process cartridge of the present invention. The photoconductor 201 is built in, and includes a charging unit 202, a developing unit 204, a transfer unit 208, and a cleaning unit 207, and further includes other units as necessary. In FIG. 1, reference numeral 203 denotes exposure by exposure means, and 205 denotes a recording medium.

  As the photosensitive member 201, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging unit 202.

  Next, an image forming process using the process cartridge shown in FIG. 1 will be described. As the photosensitive member 201 rotates in the direction of the arrow, an electrostatic latent image corresponding to the exposure image is formed on the surface by charging by the charging unit 202 and exposure 203 by the exposure unit (not shown). The electrostatic latent image is developed by the developing unit 204, and the toner image is transferred to the recording medium 205 by the transfer unit 208 and printed out. Next, the surface of the photosensitive member 201 after the transfer is cleaned by the cleaning unit 207, and is further neutralized by the neutralizing unit (not shown), and the above operation is repeated again.

  The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Furthermore, the image forming apparatus of the present invention preferably includes a photosensitive member and a cleaning unit that cleans the toner remaining on the photosensitive member and / or the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member.

  The image forming apparatus according to the present invention may be configured by integrally combining a photosensitive member and components such as a developing unit and a cleaning unit as a process cartridge, and the process cartridge may be configured to be detachable from the image forming apparatus main body. Good. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is integrally supported together with a photosensitive member to form a process cartridge, and is detachable from the image forming apparatus main unit The image forming apparatus main body may be configured to be detachable using guide means such as rails.

  The image forming apparatus of the present invention comprises at least a photosensitive member, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and other units appropriately selected as necessary. For example, it is preferable to include a static elimination unit, a cleaning unit, a recycling unit, a control unit, and the like.

  The photoconductor is not particularly limited as to the material, shape, structure, size, and the like, and can be appropriately selected from known ones. Preferred examples of the shape include a drum shape and a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable from the viewpoint of long life.

  As an amorphous silicon photoreceptor, for example, a support is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is formed on the support. A photoreceptor having a photoconductive layer made of amorphous silicon formed by a film method can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an amorphous silicon deposited film on a support is preferable.

  The electrostatic latent image can be formed on the photosensitive member by, for example, charging the surface of the photosensitive member and then performing imagewise exposure, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming unit includes, for example, at least a charging unit that charges the surface of the photoconductor and an exposure unit that exposes the surface of the photoconductor imagewise.

  Charging can be performed, for example, by applying a voltage to the surface of the photoreceptor using a charging unit.

  The charging means is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging means includes a conductive or semiconductive roller, a brush, a film, a rubber blade, etc., which is known per se. Non-contact charger using corona discharge such as a charger, corotron and scorotron.

  The shape of the charging means may take the form of a magnetic brush, fur brush or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.

  The charging unit is not limited to the contact type charger as described above, but it is preferable to use a contact type charger because an image forming apparatus in which ozone generated from the charger is reduced can be obtained. .

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using an exposure unit. The exposure means is not particularly limited as long as the surface of the photoreceptor charged by the charging means can be exposed like an image to be formed, and can be appropriately selected according to the purpose. Various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system are listed.

  The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by a developing unit. The developing means is not particularly limited as long as it can be developed using, for example, the toner of the present invention, and can be appropriately selected from known ones. Preferable examples include those having at least a developing unit capable of applying toner to an image in a contact or non-contact manner.

  The developing means includes a developing roller that carries toner on a peripheral surface, rotates in contact with the photosensitive member, supplies toner to an electrostatic latent image formed on the photosensitive member, and performs development. An embodiment having a thin layer forming member that contacts the surface and thins the toner on the developing roller is preferable.

  The developing means may be of a dry development type, may be of a wet development type, may be a single color developer, or may be a multicolor developer. For example, a toner having a stirrer that frictionally stirs toner to be charged and a rotatable magnet roller is preferable.

  As the developing roller, either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By subjecting the metal roller to blasting, a developing roller having an arbitrary surface friction coefficient can be produced relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

  As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the layer regulating member. The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. In addition, since a developing bias for forming an electric field between the developing roller and the photosensitive member is applied to the developing roller, the elastic rubber layer is set to have a resistance value of 103 to 1010Ω. The developing roller rotates in the clockwise direction and conveys the toner held on the surface to a position facing the layer regulating member and the photoconductor.

  The layer regulating member is provided at a position lower than the contact position between the supply roller and the developing roller. The layer regulating member is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller with a pressing force of 10 to 40 N / m. The toner that has passed through is thinned and charged by frictional charging. Further, in order to assist frictional charging, the layer regulating member is applied with a regulating bias having a value offset in the same direction as the toner charging polarity with respect to the developing bias.

  The rubber elastic body constituting the surface of the developing roller is not particularly limited and may be appropriately selected depending on the intended purpose.For example, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, Examples thereof include acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.

  The developing roller is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

  FIG. 2 shows the developing means used in the present invention together with the vicinity of the photoreceptor 101. In the developing device 100, the toner in the toner hopper 102 is supplied onto the developing roller 104 by the replenishing roller 103. The toner supplied onto the developing roller 104 is charged by friction between the developing roller 104 and the thin layer forming member. The toner that has not been consumed for development is peeled off from the developing roller 104 by the replenishing roller 103 and returned to the toner hopper 102. Further, the inside of the toner hopper 102 is stirred by the agitator 105, and the toner is kept in a uniform state. In FIG. 1, reference numeral 106 denotes a cleaning unit.

  The transfer can be performed, for example, by charging the photoreceptor, and can be performed by a transfer unit. The transfer unit preferably includes a primary transfer unit that forms a transfer image by transferring a toner image onto an intermediate transfer member, and a secondary transfer unit that transfers the transfer image onto a recording medium. At this time, two or more colors, preferably full color toner is used as the toner, and a primary transfer means for transferring the toner image onto the intermediate transfer member to form a composite transfer image; and the composite transfer image on the recording medium. An embodiment having secondary transfer means for transferring is more preferable.

  The intermediate transfer member is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the photoreceptor toward the recording medium. There may be one transfer means, or two or more transfer means. Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

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

  The fixing can be performed, for example, on the toner image transferred to the recording medium using a fixing unit, and may be performed each time the toner image of each color is transferred to the recording medium. The toner images may be stacked at the same time in a stacked state.

  The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

  In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization can be performed, for example, by applying a neutralization bias to the photosensitive member, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the photoconductor, and can be appropriately selected from known neutralizers. For example, a neutralizing lamp is preferable.

  Cleaning can be suitably performed, for example, by removing the toner remaining on the photoreceptor by a cleaning means. The cleaning means is not particularly limited and may be any one selected from known cleaners as long as it can remove the toner remaining on the photosensitive member. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or a magnetic roller can be selected. A cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

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

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

  FIG. 3 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a photoconductor 2 that is driven to rotate in the clockwise direction in FIG. 3 is housed in a main body housing (not shown). A charging unit 3 and an exposure unit are disposed around the photoconductor 2. 4, a developing unit 5, a transfer unit 6, a cleaning unit 13, a charge eliminating unit 8, and the like.

  The image forming apparatus includes a paper feeding cassette (not shown) that stores a plurality of recording papers. The recording paper in the paper feeding cassette is formed by a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the sheet is sent out between the transfer unit 6 and the photosensitive member 2.

  The image forming apparatus rotates the photosensitive member 2 in the clockwise direction in FIG. 3, uniformly charges the photosensitive member 2 with the charging unit 3, and then irradiates a laser modulated with image data by the exposing unit 4. Then, an electrostatic latent image is formed on the photosensitive member 2, and toner is attached to the photosensitive member 2 on which the electrostatic latent image is formed by the developing means 5 and developed. Next, the recording paper is conveyed between the photosensitive member 2 on which the toner image is formed by the developing unit 5 and the transfer unit 6, thereby transferring the toner image to the recording paper. Further, the recording paper on which the toner image is transferred is conveyed to a fixing unit (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats and pressurizes the recording paper conveyed from the transfer unit 6. After fixing the toner image on the recording paper to the recording paper, the toner image is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the photosensitive member 2 on which the toner image is transferred onto the recording paper by the transfer unit 6 and then scrapes and removes the toner remaining on the surface of the photosensitive member 2 by the cleaning unit 13 with a blade. Then, the charge is removed by the charge removing means 8. The image forming apparatus uniformly charges the photosensitive member 2 neutralized by the neutralizing unit 8 with the charging unit 3 and then forms the next image in the same manner as described above. The cleaning unit 13 is not limited to scraping off the residual toner on the photoconductor 2 with a blade, and for example, the cleaning unit 13 may scrape off the residual toner on the photoconductor 2 with a fur brush 502.

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. All parts refer to parts by weight.
(Production Example 1 of vinyl copolymer resin particles)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. What was dissolved in 100 parts of water was added, and 15 minutes later, a mixed solution of 60 parts of styrene, 20 parts of butyl acrylate, 20 parts of methacrylic acid, 100 parts of p-styryltrimethoxysilane, and 3.5 parts of n-octyl mercaptan Was added dropwise over 90 minutes and maintained at 80 ° C. for a further 60 minutes. Then, it cooled and the dispersion liquid of [vinyl-type copolymer resin particle V1] was obtained. The average particle size of V1 was 65 nm. The dispersion was taken up in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 11,000, the weight average molecular weight was 18000, and Tg was 60 ° C.
(Production example 2 of vinyl copolymer resin particles)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. A solution dissolved in 100 parts of water is added, and 15 minutes later, 90 parts of styrene, 20 parts of methacrylic acid, 90 parts of 3-methacryloyloxypropyltrimethoxysilane, and 3.5 parts of n-octyl mercaptan are added over 90 minutes. And then kept at 80 ° C. for 60 minutes. Then, it cooled and the dispersion liquid of [vinyl-type copolymer resin particle V2] was obtained. The average particle size of V2 was 70 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 9000, the weight average molecular weight was 15000, and the Tg was 50 ° C.
(Production Example 3 of Vinyl Copolymer Resin Particles)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. A solution dissolved in 100 parts of water is added, and after 15 minutes, 70 parts of styrene, 30 parts of methacrylic acid, 60 parts of p-styryltrimethoxysilane, 40 parts of 3-methacryloyloxypropylmethyldimethoxysilane, n-octyl mercaptan3. 5 parts of the mixture was added dropwise over 90 minutes and kept at 80 ° C. for a further 60 minutes. Then, it cooled and obtained the dispersion liquid of [vinyl-type copolymer resin particle V3]. The average particle size of V3 was 50 nm. The dispersion was taken up in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 10,000, the weight average molecular weight was 16000, and Tg was 58 ° C.
(Production Example 4 of Vinyl Copolymer Resin Particles)
Put 1.2 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, heat to 80 ° C, and then ion-exchange 2.5 parts of potassium persulfate. A solution dissolved in 100 parts of water was added, and 15 minutes later, a mixture of 154 parts of styrene, 30 parts of butyl acrylate, 16 parts of methacrylic acid, and 3.4 parts of n-octyl mercaptan was added dropwise over 90 minutes. Maintained at 80 ° C. for 60 minutes. Then, it cooled and obtained the dispersion liquid of [vinyl-type copolymer resin particle V4]. The average particle size of V4 was 90 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 13,000, the weight average molecular weight was 24,000, and Tg was 68 ° C.
(Production Example 5 of vinyl copolymer resin particles)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion-exchanged water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion-exchanged. A solution dissolved in 100 parts of water is added, and 15 minutes later, a mixed solution of 60 parts of styrene, 20 parts of butyl acrylate, 20 parts of methacrylic acid, 100 parts of trimethylsilyl methacrylate and 3.5 parts of n-octyl mercaptan is added for 90 minutes. The solution was added dropwise and kept at 80 ° C. for 60 minutes. Then, it cooled and obtained the dispersion liquid of [vinyl-type copolymer resin particle V5]. The average particle size of V5 was 65 nm. The dispersion was taken up in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. As a result, the number average molecular weight was 11,000, the weight average molecular weight was 18000, and Tg was 60 ° C.
(Production Example 1 of Vinyl Copolymer Resin Ethyl Acetate Solution)
Using a Spectra / Por regenerated cellulose dialysis tube (fractional molecular weight 3500, diameter 34 mm) manufactured by Spectrum, the aqueous dispersion 200 g of the vinyl copolymer resin fine particles V1 prepared in Production Example 1 of the vinyl copolymer resin particles was used. It was immersed for 24 hours at room temperature in a 10 L container into which ion-exchanged water was poured and overflowed. Subsequently, the resin particles were reprecipitated with 5 L of ethanol and separated, and then a 25 wt% vinyl copolymer resin ethyl acetate solution X1 was prepared.
(Production Example 2 of Vinyl Copolymer Resin Ethyl Acetate Solution)
The vinyl copolymer resin particles V2 were treated in the same manner as in Production Example 1 of the vinyl copolymer resin ethyl acetate solution X1 to obtain a 25 wt% vinyl copolymer resin ethyl acetate solution X2.
(Manufacture example 1 of a master batch)
Carbon Black Legal 400R (Cabot) 40 parts, Polyester Resin RS-801 (Sanyo Kasei Co., Ltd.) (acid value 10 mg KOH / g, Mw 20000, Tg 64 ° C.) 60 parts, water 30 parts are mixed with a Henschel mixer, pigment A mixture with water soaked into the aggregate was obtained. This was kneaded for 45 minutes with two rolls with the roll surface temperature set at 130 ° C., and pulverized to a mean particle size of 1 mm with a pulverizer to obtain [Masterbatch 1].
(Manufacture example 2 of a master batch)
40 parts of C.I. I. Pigment Blue 15: 3, 60 parts of polyester resin RS-801 (manufactured by Sanyo Chemical Co., Ltd.) and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls with the roll surface temperature set at 130 ° C., and pulverized to a mean particle size of 1 mm with a pulverizer to obtain [Masterbatch 2].
(Manufacture example 3 of a master batch)
40 parts of C.I. I. Pigment Red 57: 1, 60 parts of polyester resin RS-801 (manufactured by Sanyo Chemical Co., Ltd.) and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls with the roll surface temperature set at 130 ° C., and pulverized to a mean particle size of 1 mm with a pulverizer to obtain [Masterbatch 3].
(Manufacture example 4 of a master batch)
40 parts of C.I. I. Pigment Yellow 180, polyester resin RS-801 (manufactured by Sanyo Chemical Co., Ltd.) 60 parts, and water 30 parts were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a mean particle diameter of 1 mm with a pulverizer to obtain [Masterbatch 4].
Example 1
In a reaction vessel equipped with a cooling pipe, 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, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at normal pressure and 230 ° C. for 8 hours, and further reacted under 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 mgKOH / g, and a hydroxyl value of 49 mgKOH / g.

  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. Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

  In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyltin Add 2 parts of oxide, react at normal pressure and 230 ° C for 8 hours, and further react for 5 hours under reduced pressure of 10 to 15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel at 180 ° C and normal pressure. By reacting for 2 hours, [Polyester 1] was obtained. [Polyester 1] had a weight average molecular weight of 4000, Tg of 43 ° C., and an acid value of 25 mgKOH / g.

  In a container equipped with a stir bar and thermometer, 543.5 parts of [Polyester 1], 181 parts of paraffin wax, and 1450 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and held at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 2] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [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), zirconia beads having a liquid feed speed of 1 kg / hour, a disk peripheral speed of 6 m / second, and a particle diameter of 0.5 mm. 80% by volume, and the cyan pigment and wax were dispersed under the condition of 3 passes. Next, 655 parts of a 65% by weight 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]. [Pigment / Wax Dispersion 1] was prepared by adding ethyl acetate so that the solid content concentration (measurement conditions: 130 ° C., 30 minutes) was 50% by weight.

968 parts of ion-exchanged water, 40 parts of a 25% by weight aqueous dispersion of resin fine particles for dispersion stabilization (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), dodecyl diphenyl ether 150 parts of a 48.5% by weight aqueous solution of sodium disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 98 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated [Aqueous Phase 1].
[Pigment / Wax Dispersion 1] 976 parts and 2.6 parts of isophoronediamine as amines were mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), and [Prepolymer 1] 88 parts were added and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika). Furthermore, 1200 parts of [Aqueous phase 1] was added and mixed for 15 minutes at 8000 to 13000 rpm using a TK homomixer to obtain [Emulsified slurry 1].

  [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].

  To [Dispersion Slurry 1], the dispersion of [Vinyl Copolymer Resin Particles V1] was added at a solid content ratio of 1: 0.12, and heated to 73 ° C. over 30 minutes. A solution prepared by dissolving 100 parts of magnesium chloride hexahydrate in 100 parts of ion-exchanged water was kept at 70 ° C. while adding little by little. After 4 hours, an aqueous hydrochloric acid solution was added to adjust the pH to 5, followed by heating to 80 ° C. After 2 hours, the mixture was cooled to obtain [Dispersed slurry 1A].

[Dispersion slurry 1A] 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 (12000 rpm for 10 minutes), and then filtered.
(2) 900 parts of ion-exchanged water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μS / cm or less.
(3) 10% by weight hydrochloric acid was added so that the pH of the reslurry liquid of (2) was 4, and the mixture was stirred as it was with a three-one motor and filtered after 30 minutes.
(4) 100 parts of ion exchanged water was added to the filter cake of (3), mixed with a TK homomixer (12000 rpm for 10 minutes), and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μS / cm or less to obtain [Filter Cake 1].

[Filter cake 1] was dried for 48 hours at 45 ° C. using a circulating dryer, and sieved with a mesh of 75 μm to obtain [Base particle 1]. The volume average particle diameter (Dv) is 7.2 μm, the number average particle diameter (Dp) is 6.2 μm, Dv / Dp is 1.16, the average circularity is 0.975, and the film thickness of the shell is 0.13 μm. Met. Next, 100 parts of [base particle 1], 1.0 part of hydrophobic silica H20TM (manufactured by Clariant) and 0.5 part of hydrophobic silica NX90 (manufactured by Nippon Aerosil Co., Ltd.) are mixed with a Henschel mixer, and nonmagnetic A toner was obtained.
(Example 2)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that V2 was used as the vinyl copolymer resin particles. The volume average particle diameter (Dv) is 6.8 μm, the number average particle diameter (Dp) is 6.0 μm, Dv / Dp is 1.13, the average circularity is 0.978, and the film thickness of the shell material is 0.00. It was 12 μm.
(Example 3)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that V3 was used as the vinyl copolymer resin particles. The volume average particle diameter (Dv) is 7.4 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.14, the average circularity is 0.972, and the film thickness of the shell is 0.14 μm. Met.
Example 4
The nonmagnetic toner was added to [Dispersion Slurry 1] in the same manner as in Example 1 except that the dispersion of [Vinyl Copolymer Resin Particle V1] was added at a solid content ratio of 1: 0.05. Obtained. The volume average particle diameter (Dv) is 7.1 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.09, the average circularity is 0.980, and the film thickness of the shell is 0.05 μm. Met.
(Example 5)
The nonmagnetic toner was added to [Dispersion Slurry 1] in the same manner as in Example 1 except that the dispersion of [Vinyl Copolymer Resin Particle V1] was added at a solid content ratio of 1: 0.24. Obtained. The volume average particle size (Dv) is 7.3 μm, the number average particle size (Dp) is 6.1 μm, Dv / Dp is 1.20, the average circularity is 0.968, and the film thickness of the shell is 0.26 μm. Met.
(Example 6)
The nonmagnetic toner was added to [Dispersion Slurry 1] in the same manner as in Example 1 except that the dispersion of [Vinyl Copolymer Resin Particle V1] was added at a solid content ratio of 1: 0.12. Obtained. The volume average particle diameter (Dv) is 5.3 μm, the number average particle diameter (Dp) is 4.8 μm, Dv / Dp is 1.10, the average circularity is 0.981, and the film thickness of the shell is 0.10 μm. Met.
(Example 7)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that the addition amount of Eleminol MON-7 (manufactured by Sanyo Chemical Industries) was 100 parts. The volume average particle diameter (Dv) is 9.6 μm, the number average particle diameter (Dp) is 8.4 μm, Dv / Dp is 1.14, the average circularity is 0.973, and the film thickness of the shell is 0.17 μm. Met.
(Example 8)
Change [Masterbatch 1] to [Masterbatch2], and add [Vinyl copolymer resin particle V1] dispersion to [Dispersion slurry 1] so that the solid content ratio is 1: 0.1. Base particles 8] were prepared, 100 parts of [Base particles 8], 0.2 parts of hydrophobic silica H20TM (manufactured by Clariant), and 0.5 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) Are mixed with a Q-type mixer to obtain [base particles 8A]. Next, 100 parts of [base particle 8A], 1.0 part of hydrophobic silica H20TM (manufactured by Clariant) and 0.5 part of hydrophobic silica NX90 (manufactured by Nippon Aerosil Co., Ltd.) are mixed with a Henschel mixer. In the same manner as in Example 1, a nonmagnetic toner was obtained. The volume average particle diameter (Dv) is 7.5 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.15, the average circularity is 0.972, and the film thickness of the shell is 0.12 μm. Met.
Example 9
[Masterbatch 1] was changed to [Masterbatch 3], and a nonmagnetic toner was obtained in the same manner as in Example 8 except that V2 was used as the vinyl copolymer resin particles. The volume average particle diameter (Dv) is 7.0 μm, the number average particle diameter (Dp) is 6.2 μm, Dv / Dp is 1.13, the average circularity is 0.978, and the film thickness of the shell is 0.11 μm. Met.
(Example 10)
[Masterbatch 1] was changed to [Masterbatch 4], and a nonmagnetic toner was obtained in the same manner as in Example 8 except that V3 was used as vinyl copolymer resin particles. The volume average particle diameter (Dv) is 7.6 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.17, the average circularity is 0.971, and the film thickness of the shell is 0.12 μm. Met.
( Reference Example 11)
The nonmagnetic toner was added to [Dispersion Slurry 1] in the same manner as in Example 1 except that the dispersion of [Vinyl Copolymer Resin Particles V1] was added at a solid content ratio of 1: 0.01. Obtained. The volume average particle diameter (Dv) is 7.3 μm, the number average particle diameter (Dp) is 6.2 μm, Dv / Dp is 1.18, the average circularity is 0.967, and the shell material thickness is 0.01 μm. Met.
( Reference Example 12)
To [Dispersion Slurry 1], the dispersion of [Vinyl Copolymer Resin Particle V1] was added to a solid content ratio of 1: 0.5, adjusted to pH 5, heated to 80 ° C., and cooled after 4 hours. A nonmagnetic toner was obtained in the same manner as Example 1 except for the above. The volume average particle diameter (Dv) is 8.1 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.25, the average circularity is 0.987, and the film thickness of the shell is 0.49 μm. Met.
(Example 13)
To [Dispersion Slurry 1], the dispersion of [Vinyl Copolymer Resin Particles V1] was added to a solid content ratio of 1: 0.12, adjusted to pH 5, and then cooled at 70 ° C. for 2 hours. In the same manner as in Example 1, a nonmagnetic toner was obtained. The volume average particle diameter (Dv) is 7.4 μm, the number average particle diameter (Dp) is 5.8 μm, Dv / Dp is 1.28, the average circularity is 0.951, and the film thickness of the shell is 0.11 μm. Met.
(Example 14)
When preparing [Emulsified slurry], 25 wt% vinyl copolymer resin ethyl acetate solution X1 is added so that the solid content ratio becomes 1: 0.12, and ion-exchanged water is added to [Dispersed slurry 1]. A nonmagnetic toner was obtained in the same manner as in Example 1 except that only 100 parts were added and heated. The volume average particle diameter (Dv) was 7.0 μm, the number average particle diameter (Dp) was 5.9 μm, Dv / Dp was 1.19, and the average circularity was 0.978. The vinyl copolymer resin dissolved in X1 was observed in the same manner as the film thickness measurement. As a result, a substantially uniform shell material part was formed, and the film thickness was 0.12 μm.
(Example 15)
A nonmagnetic toner was obtained in the same manner as in Example 14 except that 25 wt% vinyl copolymer resin ethyl acetate solution X2 was used. The volume average particle diameter (Dv) is 7.5 μm, the number average particle diameter (Dp) is 6.4 μm, Dv / Dp is 1.17, the average circularity is 0.976, and a substantially uniform shell part is formed. The film thickness was 0.13 μm.
(Comparative Example 1)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that V4 was used as the vinyl copolymer resin particles. The volume average particle diameter (Dv) is 7.4 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.14, the average circularity is 0.971, and the film thickness of the shell is 0.13 μm. Met.
(Comparative Example 2)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that [Dispersion Slurry 1] was used instead of [Dispersion Slurry 1A]. The volume average particle diameter (Dv) was 7.6 μm, the number average particle diameter (Dp) was 6.5 μm, Dv / Dp was 1.17, and the average circularity was 0.975. In addition, the shell material part was not observed.
(Comparative Example 3)
A nonmagnetic toner was obtained in the same manner as in Example 1 except that V5 was used as the vinyl copolymer resin particles. The volume average particle diameter (Dv) is 7.5 μm, the number average particle diameter (Dp) is 6.5 μm, Dv / Dp is 1.15, the average circularity is 0.974, and the film thickness of the shell is 0.14 μm. Met.
(Evaluation method and evaluation results)
Use a nonmagnetic toner ipsio CX2500 (manufactured by Ricoh Co., Ltd.), a fixing machine with a fixing belt linear velocity of 125 mm / sec and a fixing belt temperature of 170 ° C., and a B / W ratio of 5%. The print pattern was continuously printed in a high temperature and high humidity environment H / H (30 ° C., 80% RH) and a low temperature and low humidity environment L / L (10 ° C., 15% RH).
(durability)
(A) Charge amount After printing 50 sheets and 2000 sheets continuously under H / H and L / L environments, the toner on the developing roller during blank pattern printing is sucked, and the charge amount is measured with an electrometer to obtain 50 sheets. The charge amount difference ΔQ after and after 2000 sheets was evaluated.

○: Absolute value of ΔQ is less than 10 μC / g Δ: Absolute value of ΔQ is 10 μC / g or more and less than 15 μC / g ×: Absolute value of ΔQ is 15 μC / g or more (b) Soil H / H and L / L environments After 2000 continuous printings were performed below, ΔE of the background toner was determined by a tape transfer method. The tape transfer method is a method in which a mending tape (manufactured by Sumitomo 3M) is affixed onto the toner existing on the photoconductor to transfer fog toner onto the tape. This is a method in which each is pasted on white paper, the reflection density thereof is measured by X-Rite 939, and the difference ΔE is obtained as the reflection density of the background stain.

○: The absolute value of ΔE is less than 3 Δ: The absolute value of ΔE is 3 or more and less than 6 ×: The absolute value of ΔE is 6 or more (fixing separation property)
After continuous printing of 2000 sheets in an H / H environment, the fixing separation property was evaluated. The transfer paper was fixed from the end margin of 4 mm at a temperature of 10 ° C. within the range of 140 to 190 ° C. after the continuous printing of 2000 sheets, and the separable / non-offset temperature range was determined. The temperature range means a fixing temperature range in which the paper is satisfactorily separated from the heating roller and no offset phenomenon occurs.

  A: Separable / non-offset temperature range was 50 ° C. or higher.

  (Triangle | delta): The separable / non-offset temperature range was 30 degreeC or more and less than 50 degreeC.

  X: The separable / non-offset temperature range was less than 30 ° C.

  The above evaluation results are shown in Table 1.

Here, ○, Δ, and × of the background stain (overall) are evaluated in three stages as the overall result of the background stain, ○ is a very good level, Δ is a level that is not problematic in practice, and × is Each indicates a practically problematic level.

In Reference Example 11, the change in the charge amount was large, and the background contamination was reduced. This is presumably because the charge amount distribution is widened. In Reference Example 12, the fixing separation property on the high temperature side was lowered. On the other hand, in Comparative Example 1, the soiling was particularly deteriorated in the H / H environment. Further, in Comparative Example 2, the change in the charge amount was increased, and the soiling was deteriorated. Furthermore, in Comparative Example 3, the change in the charge amount became large and the soiling deteriorated particularly in the L / L environment.

  As described above, the toner of the present invention can ensure the chargeability during the durability and the stability of the charge amount distribution, and can obtain a stable fixing separation property and image quality.

FIG. 1 is a diagram showing an example of a process cartridge according to the present invention. FIG. 2 is a diagram showing an example of the developing means used in the present invention. FIG. 3 is a diagram illustrating an example of the image forming apparatus of the present invention.

Claims (23)

And base particles bets toner, the non-magnetic toner having an external additive,
The toner base particles have a core part containing at least a colorant and a first binder resin, and a shell part made of a second binder resin covering the core part,
The shell material part contains a resin having at least a silanol group,
The shell material portion has a thickness of 20 nm to 300 nm,
The non-magnetic toner, wherein the external additive contains at least particles made of silicon oxide. The nonmagnetic toner according to claim 1, wherein the shell part is formed by aggregating and fusing particles containing at least a resin having a silanol group. 3. The nonmagnetic toner according to claim 1, wherein the shell portion is formed using an aqueous dispersion in which particles containing a resin having at least a silanol group are dispersed in an aqueous medium. The silanol group has the general formula
Obtained by chemically treating the functional group represented by
R ₁ , R ₂ and R ₃ are each independently a branched or straight chain alkyl group having 1 to 6 carbon atoms, an alicyclic group having 3 to 6 carbon atoms, and substituted or unsubstituted phenyl. The nonmagnetic toner according to claim 1, which is a hydrocarbon group selected from the group consisting of groups. With body volume average particle diameter of 4μm or more 10μm or less, the non-magnetic toner according to any one of average circularity of claims 1 to 4 is 0.910 or more 0.990 or less. The nonmagnetic toner according to claim 1, wherein the first binder resin contains a polyester resin having a glass transition temperature of 40 ° C. or higher and 80 ° C. or lower. The first binder resin, a non-magnetic toner according to any one of claims 1 to 6 containing a modified polyester resin.   The non-magnetic toner according to claim 7, wherein the modified polyester resin has at least one of a urethane group and a urea group. The nonmagnetic toner according to any one of claims 1 to 8, wherein the first binder resin contains a resin obtained by reacting an amine with a polyester resin having an isocyanate group at a terminal.   The nonmagnetic toner according to any one of claims 1 to 9, wherein the toner base particles are obtained by granulating at least in an aqueous medium using an organic solvent and then removing the organic solvent.   The nonmagnetic toner according to any one of claims 1 to 10, wherein the toner base particles are obtained by granulating at least in an aqueous medium, washing with the aqueous medium, and further drying.   The nonmagnetic toner according to any one of claims 1 to 11, further comprising a release agent.   The nonmagnetic toner according to any one of claims 1 to 12, further comprising a charge control agent.   The nonmagnetic toner according to claim 1, which is used in a one-component development system.   An image forming apparatus that forms an image using the non-magnetic toner according to claim 1.   The image forming apparatus according to claim 15, which forms a multicolor image.   The image forming apparatus according to claim 15, further comprising an endless intermediate transfer unit. Having at least one of a photoconductor and a cleaning unit for cleaning the toner remaining on the photoconductor and the intermediate transfer unit,
The image forming apparatus according to claim 15, wherein the cleaning unit does not include a cleaning blade. It includes a photoreceptor, any of the cleaning means for cleaning the toner remaining on the photoreceptor and the intermediate transfer means,
The image forming apparatus according to claim 15, wherein the cleaning unit includes a cleaning blade.   The image forming apparatus according to claim 15, further comprising a fixing unit that fixes an image using a roller having a heating device.   21. The image forming apparatus according to claim 15, further comprising a fixing unit that fixes an image using a belt having a heating device.   The image forming apparatus according to claim 15, further comprising a fixing unit that does not require oil application to the fixing member.   An image forming apparatus that at least integrally supports a photoconductor and a developing unit that develops the electrostatic latent image formed on the photoconductor using the nonmagnetic toner according to any one of claims 1 to 14. A process cartridge which is detachable from the main body.