JP5761559B2 - Toner resin, toner using the toner resin, and developer using the toner - Google Patents

Description

  The present invention relates to a toner resin suitable for production of toner for use in electrophotographic image formation such as copying machines, electrostatic printing, printers, facsimiles, and electrostatic recording, toner using the toner resin, and the toner The present invention relates to a developer containing

  Conventionally, most of the binder resins that occupy more than 70% of the constituent components of the toner are made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, the large consumption of petroleum resources and the release of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a plant-derived resin that grows by taking in carbon dioxide in the atmosphere is used as the binder resin, the resulting carbon dioxide will only circulate in the environment, which simultaneously raises the problem of global warming and the depletion of petroleum resources. Various toners using such plant-derived resins as binder resins have been proposed. For example, it has been proposed to use polylactic acid as a binder resin.

  Since polylactic acid has high crystallinity only in the L form or the D form, the solubility in an organic solvent is extremely low, and it is difficult to use a toner production method such as a dissolved resin suspension method. On the other hand, Patent Document 1 discloses that the L-form and D-form of polylactic acid are mixed to reduce crystallinity, thereby improving the solubility in an organic solvent. However, when polylactic acid is used alone, in addition to the glass transition temperature being 60 ° C or lower, the glass transition point and the heat distortion temperature are lowered due to moisture absorption, and transport and storage under high temperature and high humidity are performed. In this case, the particles or the formed image are stuck, and there is a disadvantage that it cannot be used.

Therefore, in order to use polylactic acid as a binder resin for toner, it is necessary to modify the resin. In this regard, in Patent Document 2, copolymerized polylactic acid is obtained by reacting a reaction product of an aromatic dicarboxylic acid and an aliphatic diol with lactic acid. However, polylactic acid obtained by this method still has a glass transition temperature. Therefore, it is not possible to obtain a toner that can withstand transportation and storage at high temperatures. In the method described in Patent Document 3, copolymerized polylactic acid having a fluorene skeleton introduced therein is synthesized, and the glass transition temperature is improved to 60 ° C. or higher. However, since fluorene has the property of exhibiting fluorescence under ultraviolet light irradiation, there is a problem that it is not suitable for use as an image forming toner.
Further, in the method described in Patent Document 4, a method for developing a toner having excellent heat resistance while maintaining low-temperature fixing by giving a branched skeleton to a polymer chain is shown. It is applied to polymers formed from acrylic monomers and is not applied to polylactic acid resins.

  As described above, a toner containing polylactic acid, having good heat-and-moisture storage stability, and excellent low-temperature fixability has not yet been obtained, and further improvement and development are desired. Currently.

  An object of the present invention is to solve the above-mentioned conventional problems, and to provide a toner resin capable of producing a toner having good wet heat storage resistance and excellent low-temperature fixability. It is another object of the present invention to provide a toner using the resin for toner and a developer containing the toner.

(1) An organic solvent-soluble toner resin containing a polyhydroxycarboxylic acid skeleton, the structure of which is represented by the following formula (I), and the following X precursor has a branched polyfunctional group: a, aromatic compound or heterocyclic compound, a precursor monofunctional below Z, aromatics or polycyclic structure compound der toner resin characterized by Rukoto.
X- (Y-Z) n (I)
In the formula (I), X and Z represent a rigid skeleton having a planar structure, Y represents a polyhydroxycarboxylic acid skeleton, and n represents an integer of 2 or more.
(2) The toner resin according to (1) above, wherein the toner resin has a glass transition temperature of 50 ° C. or higher and a softening point by a 1/2 method using a flow tester is 120 ° C. or lower. resin.
( 3 ) The toner according to (1) or (2) above, wherein the polyhydroxycarboxylic acid skeleton is obtained by (co) polymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms. Resin.
( 4 ) The toner resin as described in ( 3 ) above, wherein the hydroxycarboxylic acid is lactic acid.
( 5 ) The toner resin according to any one of (1) to ( 4 ), wherein the polyhydroxycarboxylic acid skeleton is obtained by ring-opening polymerization of lactide.
( 6 ) The toner resin as described in ( 5 ) above, wherein the lactide is a mixture of L-lactide and D-lactide.
( 7 ) The toner resin according to any one of (1) to ( 6 ), wherein the polyhydroxycarboxylic acid skeleton is a polylactic acid skeleton.
( 8 ) In the polylactic acid resin composition having the polylactic acid skeleton, the optical purity X (%) in terms of a monomer component represented by the following formula (II) is 80% or less. The resin for toner according to ( 7 ).
X (%) = | X (L-form) -X (D-form) | (II)
[However, in the formula (II), X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ]
( 9 ) A toner produced using the toner resin according to any one of (1) to ( 8 ).
( 10 ) A developer comprising at least the toner described in ( 9 ) above.

  According to the present invention, it is possible to obtain a toner resin capable of providing an electrophotographic toner that uses a resin for a toner containing a polyhydroxycarboxylic acid skeleton, has good wet heat storage resistance and excellent low-temperature fixability. it can. Furthermore, a toner using the resin for toner and a developer containing the toner can be provided.

It is a figure which shows typically the structure of resin used in the Example. FIG. 3 is a schematic explanatory diagram illustrating a configuration example in an embodiment of an image forming apparatus that can be used in an image forming method using toner according to the present invention. 1 is a schematic explanatory diagram illustrating a configuration example in an embodiment of a tandem type color image forming apparatus that can be used in an image forming method using toner according to the present invention. FIG. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 3. FIG. 3 is a schematic explanatory diagram illustrating a configuration example in an embodiment of a process cartridge using toner according to the present invention.

The present invention will be described in detail below.
The resin for toner according to the present invention is a resin for toner containing a polyhydroxycarboxylic acid skeleton that is soluble in an organic solvent, and its structure is represented by the following formula (I). Thereby, physical properties such as a glass transition point of the resin can be controlled.
X- (Y-Z) n (I)
In the formula (I), X and Z represent a rigid skeleton having a planar structure, Y represents a polyhydroxycarboxylic acid skeleton, and n represents an integer of 2 or more.

  The toner resin of the present invention preferably has a glass transition temperature of 50 ° C. or higher and a softening point by a 1/2 method using a flow tester of 120 ° C. or lower. The resin preferably has a glass transition temperature of 50 ° C. or higher from the viewpoint of maintaining heat-resistant storage stability when it is converted into a toner. Further, the softening point is preferably 120 ° C. or less from the viewpoint of securing low temperature fixability.

  The polyhydroxycarboxylic acid skeleton has a (co) polymerized skeleton of hydroxycarboxylic acid, and can be formed by a method of directly dehydrating condensation of hydroxycarboxylic acid or a method of ring-opening polymerization of a corresponding cyclic ester. The polymerization method is more preferably a ring-opening polymer of a cyclic ester from the viewpoint of increasing the molecular weight of the polyhydroxycarboxylic acid to be polymerized. Furthermore, a resin using a dihydric or higher polyhydric alcohol as an initiator during the polymerization exhibits an effect of improving the affinity with the colorant.

  From the viewpoint of the transparency and thermal properties of the toner, the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid, more preferably a hydroxycarboxylic acid having 2 to 6 carbon atoms, such as lactic acid or glycolic acid. , 3-hydroxybutyric acid, 4-hydroxybutyric acid, and the like. Lactic acid is particularly preferable because it exhibits an appropriate glass transition temperature and is compatible with resin transparency and colorant.

  In addition to hydroxycarboxylic acid, it is also possible to use a cyclic ester of hydroxycarboxylic acid as the raw material of the polymer. In this case, the hydroxycarboxylic acid skeleton of the resin obtained by polymerization is the hydroxycarboxylic acid constituting the cyclic ester. It becomes a polymerized skeleton. For example, the polyhydroxycarboxylic acid skeleton of a resin obtained using lactide (lactic acid lactide) is a skeleton obtained by polymerizing lactic acid.

  The precursor of X in the above formula can be used as long as it is a molecule having a rigid skeleton having a branched polyfunctional group and a planar structure, and in particular, it may be an aromatic compound or a heterocyclic compound. Among them, a heterocyclic compound is more preferable. When X has a planar structure, it acts as a rigid part, which is considered to be effective in improving heat resistance. In addition, the precursor of X means the compound before reacting with Y or the connection component mentioned later. Further, the branched polyfunctional group in the precursor of X means having two or more functional groups having reactivity with Y or a connecting component described later.

  As a molecule having a planar structure used as a precursor of X, bis (2-hydroxyethyl) terephthalate (abbreviation: BHET), bis (2-hydroxypropyl) terephthalate (abbreviation: BHPT), if bifunctional. As long as the diol compound is trifunctional, any functional group having reactivity with the polyhydroxycarboxylic acid skeleton (Y) such as an isocyanate group or an epoxy group can be used. The isocyanurate skeleton represented by the following formula is preferable from the viewpoint of improving heat resistance.

式中、Ｒ^１は後述のＹ或いは連結成分との反応性を有する官能基を持ち、炭素数が８以下のアルキル鎖を有する。

In the formula, R ¹ has a functional group having reactivity with Y or a connecting component described later, and has an alkyl chain having 8 or less carbon atoms.

  As the polyhydroxycarboxylic acid skeleton represented by Y in the above formula, known resins can be used, and examples thereof include polyglycolic acid, polylactic acid, polyhydroxybutyric acid, polymalic acid, polyεcaprolactone, and the like. Among them, the polylactic acid skeleton is preferable because it is a plant-derived resin. Polylactic acid is a polymer in which lactic acid is bonded by an ester bond, and has recently attracted attention as an environmentally friendly biodegradable plastic. In other words, in nature, enzymes that cleave ester bonds (esterases) are widely distributed, so polylactic acid is gradually decomposed by such enzymes in the environment and converted into lactic acid, which is a monomer. And eventually carbon dioxide and water.

In the polylactic acid resin composition, the optical purity X (%) in terms of monomer component represented by the following formula (II) is 80% or less, and preferably 60% or less.
X (%) = | X (L-form) -X (D-form) | (II)
[However, in the formula (II), X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ]

  Here, the method for measuring the optical purity X is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polymer or toner having a polyester skeleton is treated with pure water, 1N sodium hydroxide and isopropyl alcohol. And then hydrolyzed by heating and stirring at 70 ° C. Subsequently, the solid content in the liquid is removed by filtration and neutralized by adding sulfuric acid to obtain an aqueous solution containing L- and / or D-lactic acid decomposed from the polyester resin. The aqueous solution was measured by a high performance liquid chromatograph (HPLC) using a chiral ligand exchange type column SUMICHILAR OA-5000 (manufactured by Sumika Chemical Analysis Co., Ltd.), and a peak area S (L ) And D-lactic acid-derived peak area S (D). The optical purity X can be determined from the peak area as follows.

X (L-form)% = 100 × S (L) / (S (L) + S (D))
X (D form)% = 100 × S (D) / (S (L) + S (D))
Optical purity X% = | X (L form) -X (D form) |
Of course, the L-form and D-form used in the raw materials are optical isomers, and the optical isomers have the same physical and chemical properties other than the optical characteristics. The reactivity is equal, and the component ratio of the monomer and the component ratio of the monomer in the polymer are the same.

It is preferable for the optical purity to be 80% or less because solvent solubility and resin transparency are improved.
The X (D form) and X (L form) of the monomer that forms the hydroxycarboxylic acid skeleton are equal to the ratio of the D form and L form of the monomer used to form the hydroxycarboxylic acid skeleton. Therefore, controlling the optical purity X (%) in terms of the monomer component of the hydroxycarboxylic acid skeleton of the resin for toner can be achieved by using a proper amount of L and D monomers as monomers to obtain a racemate.

  The number average molecular weight Mn of the polyhydroxycarboxylic acid skeleton represented by Y in the above formula is preferably 1000 or more and 20000 or less. When Mn is small, the softening point is low, and the characteristics of melting quickly at low temperatures are exhibited. On the other hand, when Mn is large, the ratio of the polyhydroxycarboxylic acid unit in the toner resin is increased, so that the adhesion to paper is improved.

  The manufacturing method of polylactic acid resin is not specifically limited, A conventionally well-known method can be used. Among known production methods, for example, fermenting starch such as corn as a raw material, obtaining lactic acid, then dehydrating and condensing directly from the lactic acid monomer, or cyclic dimer lactide from lactic acid, in the presence of the catalyst There is a method of synthesis by ring-opening polymerization. Among them, the method based on the ring-opening polymerization method is preferable from the viewpoint of productivity such that the molecular weight can be controlled by the initiator amount and the reaction can be completed in a short time.

As the reaction initiator, any conventionally known alcohol component can be used regardless of the number of functional groups as long as it is an alcohol component that does not volatilize even after drying at 100 ° C. under reduced pressure of 20 mmHg or less or polymerization heating at about 200 ° C.
In the present invention, after introducing the polylactic acid resin skeleton Y using the precursor of the component Z described later as an initiator, the method of reacting with the precursor of the component X, or using the precursor of the component X as the initiator Then, after introducing the polylactic acid resin skeleton Y, a method of reacting with the precursor of the component Z can be used. Alternatively, after synthesizing polylactic acid containing Z, a method of reacting with polylactic acid containing X via a connecting component may be used.

  Examples of the connecting component include isocyanate compounds, glycidyl compounds, acid anhydride compounds, acid chloride compounds, and the like. Preferred linking components include tolylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, methylenebiscyclohexyl diisocyanate, and the like, resorcinol diglycidyl ether, neopentyl glycol Diglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl terephthalic acid, diglycidyl isophthalic acid, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, poly Diglycidyl ethers such as lopyrene glycol diglycidyl ether, naphthalene tetracarboxylic anhydride, dioxotetrahydrofuranylmethylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, oxydiphthalic anhydride, biphenyltetracarboxylic anhydride, benzophenone tetracarboxylic acid Acid anhydrides such as anhydride, diphenylsulfonetetracarboxylic acid anhydride, tetrafluoroisopropylidenediphthalic acid anhydride, terphenyltetracarboxylic acid anhydride, cyclobutanetetracarboxylic acid anhydride, carboxymethylcyclopentanetricarboxylic acid anhydride, Aliphatic carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid And acid chlorides thereof. When the connecting component is an isocyanate compound, the isocyanate group reacts with the hydroxy group of the polyhydroxycarboxylic acid skeleton (Y) to form a urethane bond, which is preferable. Of these, diisocyanate is particularly preferable because of its high reactivity and easy handling. Furthermore, aromatic diisocyanate is most suitable because of its high reactivity and high effect of preventing a decrease in Tg. Of these, isophorone diisocyanate (abbreviation: IPDI) is preferable from the viewpoint of reactivity and safety.

The precursor of Z in the above formula can be used as long as it is a monofunctional, rigid skeleton molecule having a planar structure, but it has a polycyclic structure skeleton having many ring structures and an aromatic ring. A structure is preferred. In addition, the precursor of Z means the compound before reacting with said Y or a connection component. In addition, that the Z precursor is monofunctional means that it has only one functional group having reactivity with the Y or the connecting component.
Examples of such skeletons are given below. Examples of the polycyclic structure skeleton include polycyclic aromatic heterocyclic compounds such as quinoline, benzofuran, and acridine, a dehydroabietic acid skeleton, and a steroid skeleton. In addition, examples of the structure having other aromatic rings include polycyclic aromatic compounds such as naphthalene and anthracene. Among these, cholesterol, which is a kind of steroid, is preferable in consideration of being derived from a natural product.

  In the present invention, an esterification catalyst or a urethanization catalyst such as an amine compound, a tin compound, or a titanium compound may be used to promote various polymerization reactions. However, since the urethanization catalyst may act as a decomposition catalyst in the resin, it is preferable not to use it at all or to reduce the amount used.

  Furthermore, in the present invention, a known heat stabilizer, antioxidant, ultraviolet absorber, flame retardant, non-reactive hydrolysis inhibitor, light resistance improver, if necessary, during the resin polymerization process and / or after polymerization. In addition to wax, lubricant, charge control agent, organic plasticizer, other biodegradable thermoplastic resins, various additives such as colorants and matting agents may be added as appropriate.

-Toner production method-
Next, a toner manufacturing method in the present invention will be described.
In the production of the toner in the present invention, any known production method such as a dry production method such as a kneading and pulverization method or a wet production method such as an agglomeration coalescence method can be used. However, polylactic acid is a hard resin. Since the energy required for pulverization increases, it is preferable to use a wet manufacturing method.

  Hereinafter, examples of the toner production method in the present invention include a kneading pulverization method, an emulsion aggregation method, a dissolution suspension method, a dissolution emulsion method, a suspension granulation method, a suspension polymerization method, an ester elongation method, and the like. This will be described in more detail.

<Kneading and grinding method>
In the case of the kneading and pulverizing method, it includes a pre-mixing step of Step 1, a melt-kneading step of Step 2, a pulverizing step of Step 3, and a classification step of Step 4.
Below, each manufacturing process of step 1-step 4 is demonstrated in detail.

(Pre-mixing process)
In the pre-mixing step of Step 1, at least a binder resin, a colorant and hydrophobic fine particles are dry-mixed with a mixer to prepare a mixture. The mixture may contain other toner additive components in addition to the binder resin, colorant and hydrophobic fine particles. Examples of other toner additive components include the aforementioned release agent (wax), charge control agent, and the like.
A known mixer can be used for dry mixing. For example, a Henschel mixer (trade name: FM mixer, manufactured by Mitsui Mining Co., Ltd.), a super mixer (trade name, manufactured by Kawata Co., Ltd.), a mechano mill (product) Name, Okada Seiko Co., Ltd. and other Henschel type mixing devices, Ongmill (trade name, manufactured by Hosokawa Micron Co., Ltd.), hybridization system (trade name, manufactured by Nara Machinery Co., Ltd.), Cosmo System (trade name, Kawasaki Heavy Industries, Ltd.) Etc.).

(Melting and kneading process)
In the melt-kneading process of step 2, the mixture prepared in the pre-mixing process is melt-kneaded to prepare a melt-kneaded product. The melt kneading of the mixture is performed by heating to a temperature not lower than the softening point of the binder resin and lower than the thermal decomposition temperature, and the raw materials for the toner other than the binder resin in the binder resin by melting or softening the binder resin. To disperse.
As a kneader used for melt kneading, a known kneader can be used. For example, a general kneader such as a kneader, a twin-screw extruder, a two-roll mill, a three-roll mill, or a lab blast mill can be used. More specifically, for example, TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, PCM-30 (all of which are trade names, manufactured by Ikegai Co., Ltd.), etc. Extruders, open roll type kneaders such as MOS320-1800, Needex (all of which are trade names, manufactured by Mitsui Mining Co., Ltd.). The mixture of toner raw materials may be melt-kneaded using a plurality of kneaders.

(Crushing process)
In the pulverization step of Step 3, the melt-kneaded product obtained in the melt-kneading step is cooled and solidified, and then pulverized to produce a pulverized product. That is, the cooled and solidified melt-kneaded product is first roughly pulverized into a coarsely pulverized product having a volume average particle size of about 100 μm to 5 mm, for example, by a hammer mill or a cutting mill. Thereafter, the obtained coarsely pulverized product is further finely pulverized to, for example, a pulverized product having a volume average particle diameter of 15 μm or less.
For finely pulverizing coarsely pulverized products, for example, a jet type pulverizer that uses a supersonic jet stream, or a space formed between a rotor (rotor) and a stator (liner) that rotate at high speed. An impact pulverizer that introduces and pulverizes coarsely pulverized material can be used. The cooled and solidified melt-kneaded product may be directly pulverized by a jet pulverizer or an impact pulverizer without being coarsely pulverized by a hammer mill or a cutting mill.

(Classification process)
In the classification step of Step 4, by using a classifier from the pulverized product produced in the pulverization step, over-pulverized toner particles (hereinafter sometimes referred to as “over-pulverized product”) and coarse toner particles (hereinafter referred to as “over-pulverized product”). (Sometimes referred to as “coarse”). The excessively pulverized toner particles and coarse toner particles can be recovered and used for reuse in the production of other toners. For the classification, a known classifier capable of removing excessively pulverized toner particles and coarse toner particles by classification by centrifugal force or classification by wind force can be used. For example, a swirling wind classifier (rotary wind classifier), etc. Can be used. The classification is preferably carried out by appropriately adjusting the classification conditions so that the toner particles obtained after classification have a volume average particle diameter of 3 μm or more and 15 μm or less.

<Emulsion aggregation method>
In the case of the emulsion aggregation method, the emulsion aggregation method is produced by a method including the aggregation process in Step 1, the adhesion process in Step 2, and the fusion process in Step 3. The binder resin particles are generally produced by emulsion polymerization or the like.
(Aggregation process)
In the aggregation process of Step 1, the binder resin particles are prepared with a polymerizable monomer at the stage of preparing the binder resin particles, and the binder resin particles are dispersed in a solvent with an ionic surfactant. Subsequently, other toner constituent materials such as a colorant dispersed with an ionic surfactant having an opposite polarity are mixed to form heteroaggregation to form aggregated particles.

(Adhesion process)
In the adhesion step of Step 2, if necessary, resin particles are further added to the solution in which the resin particles are formed and adhered to the surface of the aggregated particles to form a coating layer that covers the surface of the aggregated particles. As a result, a toner having a core-shell structure can be obtained.

(Fusion process)
In the fusion process of Step 3, the aggregated particles after passing through the aggregation process or the adhesion process are heated above the glass transition point or melting point of the resin having the highest glass transition point or melting point among the binder resins contained therein. To fuse the agglomerated particles.
Thereafter, the toner is obtained through washing and drying.

In addition, as described above, the process may be performed by collectively mixing and aggregating a dispersion liquid in which various toner raw materials are dispersed, or may be a process for performing an adhesion step. . In the latter case, in the agglomeration step, the balance of the amount of the ionic dispersant of each polarity is initially shifted in advance, and for example, an inorganic metal salt such as calcium nitrate or a polymer of an inorganic metal salt such as polyaluminum chloride is used. This is ionically neutralized to form aggregated particles (core particles forming the core layer) at the glass transition point or the melting point or lower of the binder resin and stabilize them. Subsequently, a resin particle dispersion treated with a dispersing agent having a polarity and quantity that compensates for the balance deviation in the attaching step is additionally added to attach the resin particles to the surface of the core particles. Further, if necessary, after slightly heating below the glass transition point of the binder resin contained in the core particle or additional resin particle dispersion to stabilize it at a higher temperature, the additional resin particle dispersion is added. It may be fused by heating above the glass transition point of the binder resin contained in the liquid.
Further, this adhesion step may be repeated a plurality of times.

<Dissolution suspension method>
In the case of the dissolution suspension method, the binder resin, the colorant, and other components such as a release agent used as necessary are once dissolved in an organic solvent that dissolves the component such as ethyl acetate, Next, mechanical shearing force is given by a homogenizer such as a TK homomixer together with inorganic fine particles such as calcium phosphate in an aqueous solvent and an organic dispersant such as polyvinyl alcohol and sodium polyacrylate in an aqueous solvent. Disperse.
Next, the obtained dispersion is added to, for example, a 1M aqueous hydrochloric acid solution to dissolve and remove the dispersant component, followed by solid-liquid separation with Nutsche or the like using a filter paper, and then the solvent component remaining in the particles is distilled off. The toner is obtained through the process.

<Dissolution emulsification method>
In the case of the dissolution emulsification method, the binder resin component is dissolved in a solvent such as ethyl acetate, and this is subjected to mechanical shearing force by a homogenizer such as a TK homomixer in the presence of an ionic surfactant. For example, after obtaining emulsified resin particles by the surface activity of an ionic surfactant such as sodium alkylbenzene sulfonate, the remaining solvent is distilled off by distillation under reduced pressure to obtain a resin particle dispersion.
Subsequently, a toner is obtained using this resin particle dispersion in the same manner as in the emulsion aggregation method.

<Suspension granulation method>
In the case of the suspension granulation method, after prepolymerizing a polymerizable monomer, after preparing a polymer solution containing a prepolymer having a weight average molecular weight Mw of 3000 to 15000 determined from GPC (gel permeation chromatography) measurement In this solution, a coloring agent, a polymerizable monomer, a polymerization initiator, and other components such as a mold release agent as necessary are added, and then this is added in the presence of an inorganic dispersant or an organic dispersant. After suspending by applying mechanical shearing force, polymer particles can be obtained by applying thermal energy while applying stirring shear.

  In this case, it is basically the same as the suspension polymerization method, but by adjusting the weight average molecular weight Mw of the prepolymer within the range of 3000 to 15000, a viscosity suitable for fixing and granulation can be obtained. In addition, the weight average molecular weight Mw of the binder resin contained in the produced toner can be controlled without a chain transfer agent.

<Suspension polymerization method>
In the case of the suspension polymerization method, a polymerizable mixture containing a polymerizable monomer, a polymerization initiator, a colorant, a release agent, etc. is put into an aqueous medium containing a suspension stabilizer and stirred. It can be produced by forming polymer particles. More preferably, it is put into an aqueous dispersion medium system containing a polymerizable monomer, a polymerization initiator, a colorant, a release agent, a cationic polymer, an anionic dispersant, and stirred. The suspension polymerization method is preferably granulated below. In the toner granulated in this way, the release agent is encapsulated in the suspended particles, and the fixability and offset resistance are remarkably improved.

<Ester elongation method>
In the case of the ester elongation method, components such as a binder resin, a colorant, and a release agent used as necessary are dispersed in a solvent to prepare an oil phase. In addition, a particle size controlling agent and a surfactant are dispersed in water to prepare an aqueous phase. The oil phase and the aqueous phase are mixed and emulsified to form oil droplets containing wax, polyester resin, pigment and the like, and the oil droplets are converged to produce toner oil droplets having a sharp particle size distribution. In this process, an elongation reaction is simultaneously performed to form a high molecular weight resin component in the toner oil droplets. Subsequently, toner is obtained in the same manner as in the dissolution suspension method using this resin particle dispersion.

<Other ingredients>
The toner according to the present invention may further contain other components as required. Examples of other components include a charge control agent, a profiler, a colorant, a release agent, inorganic fine particles, a fluidity improver, a cleaning property improver, and a magnetic material.

<< Charge Control Agent >>
The toner according to the present invention can contain a charge control agent in the toner for the purpose of controlling the chargeability of the toner. The charge control agent is not particularly limited and includes the following materials.

  For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) and the like and lake pigments of these basic dyes, C.I. I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers and condensation polymers containing amino groups, described in JP-B No. 41-20153, JP-B No. 43-27596, JP-B No. 44-6397, JP-B No. 45-26478 Metal complex salts of monoazo dyes, and salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr described in JP-B-55-42752 and JP-B-59-7385 Gold such as Fe Genus complexes, sulfonated copper phthalocyanine pigments, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

  The content of the charge control agent is preferably 0.01 parts by mass to 2 parts by mass and more preferably 0.02 parts by mass to 1 part by mass with respect to 100 parts by mass of the binder resin. When the content is 0.01 parts by mass or more, charge controllability is obtained, and when the content is 2 parts by mass or less, the chargeability of the toner is not excessively increased and the effect of the charge control agent is reduced. In other words, the electrostatic attraction force with the developing roller is not increased, resulting in a decrease in toner fluidity and a decrease in image density.

<< Profiler >>
The toner according to the present invention may have a deforming agent for the purpose of modifying the shape of the color toner. As the deforming agent, as long as this purpose can be achieved, it can be appropriately selected according to the purpose, but a layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral with organic ions is used. It is preferable to contain. The layered inorganic mineral obtained by modifying at least part of the ions in the layered inorganic mineral that can be used as a deforming agent with organic ions is not particularly limited and may be appropriately selected depending on the intended purpose. Those having a basic crystal structure are preferably modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

  The organic cation modifier of the layered inorganic mineral in which at least some of the ions of the layered inorganic mineral are modified with organic ions is not particularly limited as long as it can be modified with organic ions in this way, and is quaternary. Examples include alkylammonium salts, phosphonium salts, imidazolium salts, and the like. Of these, quaternary alkyl ammonium salts are desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium, and the like.

  The organic anion modifier of the layered inorganic mineral in which at least part of the ions of the layered inorganic mineral is modified with organic ions is not particularly limited as long as it can be modified with organic ions as described above. Sulfates, sulfonates having branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. A carboxylate or a phosphate is mentioned. A carboxylic acid having an ethylene oxide skeleton is desirable.

  By modifying at least part of the layered inorganic mineral with organic ions, the oil phase (O1) and (O2) containing the toner composition has a moderate hydrophobicity, and has a non-Newtonian viscosity. Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05% by mass to 10% by mass, and preferably 0.05% by mass to 5% by mass. Is more preferable.

  In addition, a layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the amount added can be reduced.

  Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Preferable examples include Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (III) is more preferable. The following general formula (III) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

R ₁ (OR ₂ ) _n OSO ₃ M: general formula (III)
[In the general formula, R ₁ represents an alkyl group having 13 carbon atoms, R ₂ represents an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and M represents a monovalent metal element. ]

<< Colorant >>
In the present invention, the colorant is not particularly limited and may be appropriately selected from known colorants according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, La Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Irred, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, reed Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Lithbon, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The color of the toner colorant is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. The toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.

  Examples of black materials include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, and the like.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36, and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 10% by mass with respect to the toner mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases and the electrical characteristics of the toner. May be reduced.

  The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as such resin, According to the objective, it can select suitably from well-known things, For example, polyester, the polymer of styrene or its substitution, a styrene-type copolymer, polymethacrylic acid Methyl, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon Examples thereof include resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffin, and paraffin wax. Moreover, you may use the polyester-type resin (b1) which has polyhydroxycarboxylic acid frame | skeleton, and the point from which the compatibility of resin improves and a plant degree improve, are preferable. These may be used individually by 1 type and may use 2 or more types together.

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

<< Releasing agent >>
There is no restriction | limiting in particular as a mold release agent which can be used for the toner by this invention, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably. As these waxes, in particular, free fatty acid type carnauba wax, polyethylene wax, montan wax and oxidized rice wax can be used alone or in combination. The carnauba wax is preferably a microcrystalline wax, preferably having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30. These waxes can be used alone or in combination of two or more.

  As other mold release agents, any conventionally known mold release agents such as solid silicone wax, higher fatty acid higher alcohol, montan ester wax, polyethylene wax and polypropylene wax can be mixed and used.

  Although there is no restriction | limiting in particular as Tg of a mold release agent, 70-90 degreeC is preferable. If it is less than 70 ° C., the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 90 ° C., the releasability at a low temperature is not expressed, the cold offset resistance is deteriorated, and the paper is wound around the fixing machine. The amount of the release agent used is not particularly limited, but is 1% by mass to 20% by mass, preferably 3% by mass to 10% by mass with respect to the toner resin component. If it is less than 1% by mass, the effect of preventing offset is insufficient, and if it exceeds 20% by mass, transferability and durability are deteriorated.

<< Inorganic fine particles >>
The toner according to the present invention may have inorganic fine particles as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles.

  The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate , Zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide , Silicon nitride, and the like. These may be used individually by 1 type and may use 2 or more types together. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 2.0% by mass. Within this range, the fluidity, developability, and chargeability of the toner are improved.

<< Flowability improver >>
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a fluoride. Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Of these, silica and titanium oxide are preferably surface treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

<< Cleaning improver >>
The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, polymethyl methacrylate, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

<< Magnetic material >>
There is no restriction | limiting in particular as a magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

-Developer-
Next, the developer in the present invention will be described.
The developer contains at least the toner of the present invention and may contain other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer, but when used for a high-speed printer that supports the recent improvement in information processing speed, In view of this, a two-component developer is preferable.

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

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a copper-zinc (Cu—Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used individually by 1 type and may use 2 or more types together.

  The core material has a weight average particle diameter (D50) of preferably 10 to 200 μm, more preferably 40 to 100 μm. If the weight average particle size (D50) is less than 10 μm, the fine particle system is increased in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering, and if it exceeds 200 μm, the specific surface area decreases. Toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. Examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, and polyesters. Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and fluoride Examples include vinyl copolymers, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers (triple fluoride (multiple) copolymers), silicone resins, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, silicone resins are particularly preferable.

  There is no restriction | limiting in particular as said silicone resin, According to the objective from the silicone resin generally known, it can select suitably according to the objective, for example, straight silicone resin which consists only of organosiloxane bonds; alkyd resin, polyester Examples thereof include silicone resins modified with resins, epoxy resins, acrylic resins, urethane resins, and the like.

Examples of commercially available silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone. As modified silicone resins, KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy modified) manufactured by Toray Dow Corning Silicone Co., Ltd. ), SR2110 (alkyd modified), and the like.
It is possible to use a silicone resin alone, but it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

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

  For example, the resin layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core by a known coating method, drying, and baking. Can be formed. Examples of the application method include an immersion method, a spray method, and a brush coating method.

  There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

  The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace Etc., a method using a microwave, and the like.

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

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable mixing ratio of the toner and the carrier is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Image forming method, image forming apparatus and process cartridge)
The toner according to the present invention includes at least an electrostatic latent image forming process, a developing process, a transfer process, and a fixing process, and further, other processes appropriately selected as necessary, for example, a charge eliminating process, a cleaning process, and a recycling process. It can be used for an image forming method including a process, a control process, and the like.

  The toner according to the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. The present invention can be used for an image forming apparatus having a unit, for example, a charge eliminating unit, a cleaning unit, a recycling unit, a control unit, and the like.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”), Although it can be suitably selected from known ones, the shape is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. (OPC), and the like. Among these, amorphous silicon is preferable from the viewpoint of long life.

  The formation of the electrostatic latent image can be performed by, for example, uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be performed by electrostatic latent image forming means. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise.

  Charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charger. The charger is not particularly limited and may be appropriately selected according to the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron. Further, the charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner. Further, the charger is a charging roller that is disposed in close proximity to the electrostatic latent image carrier via a gap tape, and the surface of the electrostatic latent image carrier is obtained by applying a direct current and an alternating voltage to the charging roller in a superimposed manner. Those that charge are preferable.

  The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier imagewise using an exposure device. The exposure device is not particularly limited as long as it can be exposed like the image to be formed on the surface of the electrostatic latent image carrier charged by the charger, and can be appropriately selected according to the purpose. Examples thereof include 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. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

<Development process and development means>
The development step is a step of developing a latent image by using the toner or developer of the present invention to form a visible image. The visible image can be formed, for example, by developing an electrostatic latent image using the toner or developer 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 or developer of the present invention, and can be appropriately selected from known ones. For example, the toner or developer of the present invention can be selected. Suitable examples include those having at least a developing device that can be accommodated and can be applied to the electrostatic latent image in a contact or non-contact manner.

  The developing unit 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 developer having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically latent due to an electric attractive force. It moves to the surface of the image carrier (photoreceptor). As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the electrostatic latent image carrier (photoconductor).

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

  The transfer means (primary transfer means, secondary transfer means) has at least a transfer device that peels and charges the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. preferable. There may be one transfer means, or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. In addition, there is no restriction | limiting in particular as a recording medium, It can select suitably from well-known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or may be performed on the toner of each color. You may carry out simultaneously in the state which laminated | stacked. 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. The fixing means includes a heating body including a heating element, a film that contacts the heating body, and a pressure member that presses the heating body via the film, and is not fixed between the film and the pressure member. It is preferable that the recording medium on which an image is formed is passed and fixed by heating. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. Depending on the purpose, for example, a known optical fixing device may be used together with or instead of the fixing step and the fixing means.

<Other steps and means>
<< Static elimination process and static elimination means >>
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the electrostatic latent image carrier, and can be appropriately selected from known static neutralizers. For example, a neutralizing lamp is preferably used. Can be mentioned.

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

<< Recycling process and recycling means >>
The recycling process is a process in which the toner removed by the cleaning process is recycled to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.

<< Control process and control means >>
The control step is a step of controlling each step of the image forming method using the toner of the present invention, and can be suitably performed by the control means. The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method using the toner of the present invention by the image forming apparatus using the toner of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as an electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as a charging unit, and an exposure device 30 as an exposure unit. And a developing device 45 as a developing means, an intermediate transfer member 50, a cleaning device 60 as a cleaning means having a cleaning blade, and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow in FIG. 2 by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 such as an intermediate transfer member cleaning blade is disposed in the vicinity of the intermediate transfer member 50, and a visible image (toner image) is transferred to a recording medium 95 such as transfer paper (secondary transfer). ), A transfer roller 80 as a transfer means capable of applying a transfer bias is disposed so as to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is arranged in the rotational direction of the intermediate transfer member 50 with the photosensitive member 10, the intermediate transfer member 50, and the like. And a contact portion between the intermediate transfer member 50 and the recording medium 95.

  The developing device 45 includes a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C. The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photoreceptor 10 uniformly. The exposure device 30 performs imagewise exposure on the photoreceptor 10 to form an electrostatic latent image. The electrostatic latent image formed on the photoconductor 10 is developed by supplying toner from the developing device 45 to form a visible image (toner image). This visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto a recording medium 95 such as transfer paper. As a result, a transfer image is formed on the recording medium 95 such as transfer paper. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method using the toner of the present invention by the image forming apparatus using the toner of the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 3 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. 4 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24 that is an endless belt is stretched around a pair of rollers 23, and a recording medium (transfer paper) conveyed on the secondary transfer belt 24 and an intermediate transfer member 50. Can contact each other. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26. In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form an image on both sides of the transfer paper. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is photosensitive as shown in FIG. Based on the color body 10 (the black photoconductor 10K, the yellow photoconductor 10Y, the magenta photoconductor 10M, and the cyan photoconductor 10C), the charging device 160 that uniformly charges the photoconductor 10, and each color image information. And exposing the photosensitive member to an image corresponding to each color image (L in FIG. 4), and forming an electrostatic latent image corresponding to each color image on the photosensitive member, and the electrostatic latent image for each color image. A developing device 61 that develops using toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image Is provided with a transfer charger 62, a cleaning device 63, and a static eliminator 64 for transferring the image onto the intermediate transfer member 50, and each monochrome image (black image, yellow image) based on the image information of each color. , Magenta image, and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively a black image formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15 and 16. The yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Then, a black image, a yellow image, a magenta image, and a cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying apparatus main body 150, and abutted against the registration roller 49 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and similarly stopped against the registration roller 49. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. , And the secondary transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper) (secondary transfer), whereby the color image is transferred and formed on the sheet (recording paper). The The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the fixing color image (color transfer image) is generated by heat and pressure. ) Is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57. Alternatively, the sheet (recording paper) is switched by the switching claw 55 and reversed by the sheet reversing device 28 and returned to the transfer position. After the image is recorded on the back side, it is discharged by the discharge roller 56 and stacked on the discharge tray 57.

<Process cartridge>
The toner according to the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to form a visible image. And a developing unit that can be attached to and detached from the main body of the image forming apparatus, and can be used in a process cartridge having other means appropriately selected as necessary.

The developing means includes at least a developer container that contains the developer of the present invention and a developer carrier that carries and conveys the developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on the image forming apparatus using the toner of the present invention.

  For example, as shown in FIG. 5, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other units as necessary. It has. In FIG. 5, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.

  Next, the image forming process using the process cartridge shown in FIG. 5 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

EXAMPLES Examples and comparative examples of the present invention will be shown below, and the present invention will be described more specifically. However, the present invention is not limited to the following examples. Further, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
[Methods for measuring physical properties of components used in Examples and Comparative Examples]
(Measurement of molecular weight and residual monomer amount)
Apparatus: GPC (manufactured by Tosoh Corporation), detector: RI, measurement temperature: 40 ° C,
Mobile phase: tetrahydrofuran, flow rate: 0.45 mL / min.
The molecular weight Mn, Mw, and the molecular weight distribution Mw / Mn are respectively a number average molecular weight, a weight average molecular weight, and a molecular weight measured by GPC (gel permeation chromatography) using a calibration curve prepared with a polystyrene sample having a known molecular weight as a standard. Distribution.

(Measurement of 90% RH thermal deformation temperature)
Apparatus: TMA (manufactured by SII Nano Technology, EXSTAR7000)
Samples of 5 to 10 mg were filled in a die having a diameter of 3 mmφ and a thickness of 1 mm, compressed by a hand press, and tableted for use in measurement. Using a temperature / humidity control device attached to the device, the temperature was increased from 30 ° C. to 90 ° C. at 2 ° C./min. The temperature was increased at a pressure of 100 mN using a standard probe and the displacement was followed. Evaluation was performed by setting the peak top in the obtained thermogram to 90% RH heat distortion temperature.

(Measurement of glass transition temperature (Tg))
Device: DSC (TA Instruments, Q2000)
What filled 5-10 mg of samples in the aluminum simple airtight bread | pan was used for the following measurement flows.
1st Heating: 30 ° C. to 220 ° C., 5 ° C./min. Hold for 1 minute after reaching 220 ° C. Cooling: Quench to −20 ° C. without temperature control, hold for 1 minute after reaching −20 ° C. 2nd Heating: −20 ° C. to 180 ° C., 5 ° C./min.
The glass transition temperature was evaluated by adopting the midpoint method in the 2nd Heating thermogram and reading the value.

(Measurement of softening point)
Apparatus: Flow tester (manufactured by Shimadzu Corporation, CFT-500D)
Sample: 1.5g,
Temperature increase rate: 10 ° C / min,
Load: 10kg,
Nozzle: Diameter 0.5mm, length 1mm
Heating start temperature: 50 ° C.
Preheating time: 300 seconds,
1/2 method: The temperature at which half of the sample flowed out was taken as the softening point.

(Evaluation of organic solvent solubility)
1.5 g of the resin obtained by synthesis was stirred in 8.5 g of three solvents of ethyl acetate, tetrahydrofuran, and toluene in a 20 mL screw vial for 24 hours, and it was visually confirmed that there were no dissolved components. Those dissolved in all three solvents were judged as soluble in organic solvents.

(Production Example 1) Synthesis of Resin Precursor 1 In the flask, 85.0 parts by mass of L-lactide, 15.0 parts by mass of D-lactide, and 62 parts by mass of cholesterol as an initiator were gradually added, and the internal temperature was gradually increased. The temperature was raised and dehydration was performed under reduced pressure. Next, the temperature was further increased under N ₂ purge, and after confirming that the system was homogenized visually, 0.03 parts by mass of tin 2-ethylhexanoate was added to the system to perform a polymerization reaction. At this time, the internal temperature of the system was controlled so as not to exceed 190 ° C. After the reaction time of 2 hours passed, the system was switched to the outflow line again, unreacted lactide was removed under reduced pressure conditions, the polymerization reaction was completed, and the resin precursor 1 was obtained.

(Production Examples 2 to 9) Synthesis of Resin Precursors 2 to 9 Resin precursors were produced in the same manner as in Production Example 1 except that the types and amounts of initiators used in Production Example 1 were changed as shown in Table 1. 2-9 were synthesized.

表中の化合物Ｐ、Ｑ、Ｒは下記に示すものである。

Compounds P, Q, and R in the table are as shown below.

(Production Example 10) Synthesis of Resin Precursor 10 In Production Example 2, resin precursor 10 was synthesized by the same procedure as in Production Example 2 except that the lactide used was changed to ε-caprolactone.

Table 2 shows the molecular weights (Mn) of the obtained resin precursors 1 to 10.

(Production Example 11) Synthesis of Resin 1 85 parts by mass of resin precursor 1 was introduced into the flask, and the internal temperature was gradually raised. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Thereafter, the temperature of the system was maintained at 150 ° C., and 15 parts by mass of Compound S represented by the following formula was added and 0.20 part by mass of tin 2-ethylhexanoate was reacted to obtain Resin 1.

(Production Examples 12 to 17) Synthesis of Resins 2 to 7 In Production Example 11, the types and amounts of resins used as resin precursors and the types and amounts of materials used as skeleton X are shown in Table 3. Resins 2 to 7 were obtained by the same procedure as in Production Example 11 except for the change.

(Production Example 18) Synthesis of Resin 8 89 parts by mass of resin precursor 2 was charged into the flask, and the internal temperature was gradually raised. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Thereafter, ethyl acetate was added to 50 mass%, 0.20 parts by mass of tin 2-ethylhexanoate and 8 parts by mass of isophorone diisocyanate were added, and the system temperature was kept at 80 ° C. for reaction. Thereafter, 3 parts by mass of Compound P was added and reacted to obtain Resin 8.

(Manufacture example 19) Synthesis | combination of resin 9 39 mass parts of resin precursor 1 was thrown into the flask, and internal temperature was heated up gradually. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Then, ethyl acetate was added to 50 mass%, 0.22 parts by mass of tin 2-ethylhexanoate and 3 parts by mass of isophorone diisocyanate were added, and the system temperature was kept at 80 ° C. for reaction. Thereafter, 58 parts by mass of the resin precursor 4 was added and reacted to obtain a resin 9.

(Production Example 20) Synthesis of Resin 10 Into the flask, 81 parts by mass of the resin precursor 5 was charged, and the internal temperature was gradually raised. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Thereafter, ethyl acetate was added to 50% by mass, 0.20 parts by mass of tin 2-ethylhexanoate and 7 parts by mass of isophorone diisocyanate were added, and the system temperature was kept at 80 ° C. for reaction. Thereafter, 12 parts by mass of cholesterol was added and reacted to obtain Resin 10.

(Manufacture example 21) Synthesis | combination of resin 11 89 mass parts of resin precursor 2 was thrown into the flask, and internal temperature was heated up gradually. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Thereafter, ethyl acetate was added to 50 mass%, 0.20 parts by mass of tin 2-ethylhexanoate and 8 parts by mass of isophorone diisocyanate were added, and the system temperature was kept at 80 ° C. for reaction. Thereafter, 3 parts by mass of bis (2-hydroxyethyl terephthalate) was added and reacted to obtain Resin 11.

(Manufacture example 22) Synthesis | combination of resin 12 89 mass parts of resin precursor 2 was injected | thrown-in to the flask, and internal temperature was heated up gradually. After confirming the homogeneity of the system under visual observation, dehydration was performed under reduced pressure. Thereafter, ethyl acetate was added to 50 mass%, 0.20 parts by mass of tin 2-ethylhexanoate and 8 parts by mass of isophorone diisocyanate were added, and the system temperature was kept at 80 ° C. for reaction. Thereafter, 3 parts by mass of Compound U was added and reacted to obtain Resin 12.

The compositions of X, Y and Z in the structures of the resins 1 to 12 are as shown in Table 4. Moreover, the schematic diagram of the structure of resin 1-12 is shown in FIG.

The physical properties of the obtained resins 1 to 12 are as shown in Table 5.

Example 1 Production of Toner 1
-Creating a master batch-
The raw materials shown in Table 6 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 size of 1 mmφ with a pulverizer to obtain a master batch.

  Carnauba wax (molecular weight 1,800, acid value 2.7 mg KOH / g, penetration of 1.7 mm (40 ° C.)), master batch, charge control agent (made by Orient Chemical Industries: E- 84) was added, and the mixture was kneaded at 100 ° C. using a biaxial extruder, pulverized, and classified to obtain toner particles. Next, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain toner 1.

(Examples 2 to 12)
-Production of toners 2-12-
Toners 2 to 12 were obtained in the same manner as in Example 1 except that the type of resin used in Example 1 was changed as shown in Table 8.

(Example 13)
-Preparation of resin fine particle dispersion-
180 parts of Resin 1 and 585 parts of deionized water were placed in a stainless beaker, placed in a warm bath, and heated to 95 ° C. When the resin 1 was melted, the mixture was stirred at 8000 rpm using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and at the same time, diluted ammonia water was added to adjust the pH to 7.0.
Next, while adding 20 parts of an aqueous solution obtained by diluting 0.8 part of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), emulsification and dispersion were carried out to obtain resin fine particle dispersion 12 [resin fine particle concentration: 12. 4%] was prepared.

-Preparation of black colorant dispersion-
Carbon black legal 330: 99 parts by mass (manufactured by Cabot), 15 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), and 300 parts by mass of ion-exchanged water are mixed together, and a homogenizer (IKA) (Manufactured by Ultra Turrax T50) for 10 minutes, and then applied to a circulating ultrasonic disperser (manufactured by Nippon Seiki Seisakusho, RUS-600TCVP) to obtain a black colorant dispersion.

-Preparation of release agent dispersion-
Fischer-Tropsch wax FNP92 (melting point 92 ° C .: manufactured by Nippon Seiki Co., Ltd.), 100 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R), 400 parts by weight of ion-exchanged water, The mixture was heated to 100 ° C., sufficiently dispersed with a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion.

-Manufacture of toner 13-
105 parts of resin fine particle dispersion 12, 45 parts of black colorant dispersion, 115 parts of release agent dispersion, and 402 parts of deionized water are placed in a round stainless steel flask. Thoroughly mixed and dispersed. Next, 0.37 parts of polyaluminum chloride was added thereto, and the dispersion operation was continued with an ultra turrax.
Further, the flask was heated to 52 ° C. with stirring in an oil bath for heating. Thereafter, the pH of the system was adjusted to 8.5 with a 0.5N aqueous sodium hydroxide solution, and then the stainless steel flask was sealed, heated to 90 ° C. while continuing stirring using a magnetic seal, and maintained for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, thoroughly washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration.

This was further redispersed in 3 L of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This was repeated five more times. When the pH of the filtrate was 7.00, the electric conductivity was 8.7 μS / cm, and the surface tension was 7.08 Nm, No. Solid-liquid separation was performed using 5A filter paper, and then vacuum drying was performed for 12 hours to obtain toner base particles 13.
Next, 1.5 parts by mass of hydrophobic silica (Cabot, TS720) was added to 100 parts by mass of the toner base particles 13, and blended at 3000 rpm for 5 minutes with a Henschel mixer to obtain toner 13.

(Examples 14 and 15)
-Production of toners 14 and 15-
Toners 14 and 15 were produced in the same manner as in Example 13 except that the resins used were changed to Resins 2 and 3 in Example 13.

(Example 16)
-Preparation of aqueous medium a-
An aqueous medium a was prepared by mixing and stirring uniformly 300 parts by mass of ion-exchanged water and 0.2 parts by mass of sodium dodecylbenzene sulfonate.

-Preparation of master batch a-
1,000 parts by weight of water, 530 parts by weight of carbon black (Printex 35, manufactured by Degussa) having a DBP oil absorption of 42 ml / 100 g and a pH of 9.5, and 1200 parts by weight of Resin 1 were added to a Henschel mixer (Mitsui Mining Co., Ltd.) Mixed).
The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch a.

-Production of Toner 16-
100 parts by weight of resin 1 and 50 parts by weight of ethyl acetate were added to the reaction vessel and stirred to prepare a resin solution.
Next, 5 parts by mass of carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)) and masterbatch a 5 parts by mass were added to the resin solution. Using Viscomill (manufactured by Imex Co., Ltd.), 3 passes were carried out under the condition that the liquid feed speed was 1 kg / hour, the disk peripheral speed was 6 m / second, and 80% by volume of 0.5 mm zirconia beads were filled.
Next, 150 parts by mass of the aqueous medium a is put in the container, and 100 parts by mass of the toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was mixed for 10 minutes to obtain an emulsified slurry.
Further, 100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersion slurry a.

Next, 100 parts by mass of the dispersion slurry a was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. After adding 20 parts by mass of 10% by mass hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK homomixer, the fluorine-based quaternary ammonium salt compound, F-310 (Neos). Was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part by mass with respect to 100 parts by mass of the solid content of the toner, stirred for 10 minutes, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.

The obtained filter cake was dried at 40 ° C. for 36 hours using a circulating dryer, and sieved with a mesh having an opening of 75 μm to prepare toner mother particles 16.
Subsequently, a toner 16 was produced from the toner base particles 16 by the same procedure as in Example 13.

(Examples 17 and 18)
-Production of toners 17 and 18-
Toners 17 and 18 were produced in the same manner as in Example 16 except that the resin used was changed to Resins 2 and 3 in Example 16.

(Example 19)
-Production of aqueous dispersion of resin particles W-
In a reaction vessel equipped with a stir bar and a thermometer, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained.

The system was heated to raise the system temperature to 75 ° C. and reacted for 6 hours.
Further, 30 parts of a 1% aqueous solution of ammonium persulfate was added, and the mixture was aged at 75 ° C. for 6 hours. Fine particle dispersion, which was an aqueous dispersion of vinyl resin (a copolymer of styrene-methacrylic acid monobutyl methacrylate-alkylallylsulfosuccinic acid sodium salt) A liquid W was obtained.
The volume average particle size of the fine particle dispersion W measured by ELS-800 was 0.08 μm.
A part of the fine particle dispersion W was dried to isolate the resin component, and the glass transition temperature measured by flow tester measurement was 74 ° C.

-Preparation of aqueous medium b-
Aqueous medium b was prepared by mixing and stirring uniformly 300 parts by mass of ion-exchanged water, 300 parts by mass of fine particle dispersion W, and 0.2 parts by mass of sodium dodecylbenzene sulfonate.

-Synthesis of polyester prepolymer-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 720 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 90 parts by mass of bisphenol A propylene oxide 2-mole adduct, 290 parts by mass of terephthalic acid, anhydrous 25 parts by mass of trimellitic acid and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and then reacted for 7 hours under reduced pressure of 10 to 15 mmHg to synthesize an intermediate polyester resin.

The obtained intermediate polyester resin has a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 10,700, a peak molecular weight of 3,400, a glass transition temperature (Tg) of 57 ° C., an acid value. Of 0.4 mgKOH / g and hydroxyl value of 49 mgKOH / g.
Next, 400 parts by mass of the intermediate polyester resin, 95 parts by mass of isophorone diisocyanate, and 580 parts by mass of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 100 ° C. for 8 hours. By reacting, a polyester prepolymer was synthesized.
The obtained polyester prepolymer had a free isocyanate content of 1.42% by mass.

-Production of master batch b-
1,000 parts by weight of water, 530 parts by weight of carbon black (Printex 35, manufactured by Degussa) having a DBP oil absorption of 42 ml / 100 g and a pH of 9.5, and 1200 parts by weight of resin 1 were added to a Henschel mixer (Mitsui Mining Co., Ltd.). Mixed).
The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch b.

-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound.
The obtained ketimine compound had an amine value of 423 mgKOH / g.

-Production of Toner 19-
100 parts by mass of resin 1, 30 parts by mass of polyester prepolymer, and 80 parts by mass of ethyl acetate were added to the reaction vessel and stirred to prepare a resin solution.
Next, 5 parts by mass of carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)) and masterbatch 5 parts by mass were added to the resin solution. Using Viscomill (manufactured by Imex Co., Ltd.), 3 passes were carried out under the condition that the liquid feed speed was 1 kg / hour, the disk peripheral speed was 6 m / second, and 80% by volume of 0.5 mm zirconia beads were filled.
Further, 2.5 parts by mass of a ketimine compound was added and dissolved to obtain a toner material liquid.

Next, 150 parts by mass of an aqueous medium is put in the container, and 100 parts by mass of the toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Emulsified slurry b was obtained by mixing for minutes.
Furthermore, 100 parts by mass of the emulsified slurry b was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersion slurry b.

Next, 100 parts by mass of the dispersion slurry b was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.
To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. After adding 20 parts by mass of 10% by mass hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK homomixer, the fluorine-based quaternary ammonium salt compound, F-310 (Neos). Was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part by mass with respect to 100 parts by mass of the solid content of the toner, stirred for 10 minutes, and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.

The obtained filter cake was dried at 40 ° C. for 36 hours using a circulating dryer, and sieved with a mesh having a mesh opening of 75 μm to prepare toner mother particles 19.
Subsequently, the toner 19 was produced from the toner base particles 19 by the same procedure as in Example 13.

(Examples 20 and 21)
-Production of toners 20 and 21-
Toners 20 and 21 were produced in the same manner as in Example 19 except that the resin used was changed to Resins 2 and 3 in Example 19.

(Comparative Examples 1, 2, 3)
-Production of toners 22-24-
Toners 22 to 24 were produced in the same manner as in Example 19 except that the resin used in Example 19 was changed to resin precursors 3, 6, and 9.

Next, using the toner, the fixability and heat-resistant storage stability were evaluated as follows. The results are shown in Table 8.
<Fixability>
Plain paper and cardboard are used by changing the temperature of the fixing belt using an apparatus in which the fixing unit of an electrophotographic copying machine (MF-200, manufactured by Ricoh) is using a Teflon (registered trademark) roller as a fixing roller. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on the transfer paper type 6200 (manufactured by Ricoh Company) and copy printing paper <135> (manufactured by NBS Ricoh Company). At this time, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with thick paper with a pad was 70% or more was defined as the minimum fixing temperature. Evaluation of AC is a pass standard.

[Evaluation criteria for minimum fixing temperature]
A: Less than 135 ° C B: 135 ° C or more and less than 145 ° C C: 145 ° C or more and less than 155 ° C D: 155 ° C or more

<Moisture and heat resistance>
4 g of toner was placed in an open cylindrical container having a diameter of 5 cm and a height of 2 cm, and left for 72 hours in an environment of a temperature of 45 ° C. and a relative humidity of 65%. After leaving, the container containing the toner was shaken lightly, and the presence or absence of toner aggregation was visually observed, and the storage stability was evaluated according to the following evaluation criteria. Evaluation of AC is a pass standard.

〔Evaluation criteria〕
A: No toner aggregation observed B: 1-2 toner aggregation particles observed C: 3-5 toner aggregation particles observed D: 6 toner aggregation particles observed Observed above

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Two Next transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 42K Developer Container 42Y Developer Container 42M Developer Container 42C Developer Container 43K Developer Supply Roller 43Y Developer Supply Roller 43M Developer Supply Roller 43C Developer Supply Roller 44K Developer Roller 44Y Developer Roller 44M Developer Roller 44C Present Image roller 45 Developing device 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Corona charger 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection roller 57 Ejection tray 58 Corona charger 60 Cleaning device 61 Development device 62 Transfer charger 63 Cleaning device 64 Electrification device 70 Electrification lamp 80 Transfer roller 90 Cleaning device 95 Recording medium 100 Image forming apparatus 101 Electrostatic latent image carrier (photosensitive) body)
DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure means 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed Path 150 Copying device main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
L exposure

JP 2008-262179 A Japanese Patent Laid-Open No. 08-302003 JP 2007-112849 A JP 11-327209 A

Claims (10)

A resin for a toner containing a polyhydroxycarboxylic acid skeleton and soluble in an organic solvent, the structure of which is represented by the following formula (I), the precursor of X below has a branched polyfunctional group, an aromatic compound or heterocyclic compound, a precursor monofunctional below Z, aromatics or polycyclic structure compound der toner resin characterized by Rukoto.
X- (Y-Z) n (I)
In the formula (I), X and Z represent a rigid skeleton having a planar structure, Y represents a polyhydroxycarboxylic acid skeleton, and n represents an integer of 2 or more.   2. The toner resin according to claim 1, wherein the toner resin has a glass transition temperature of 50 ° C. or more and a softening point by a 1/2 method using a flow tester is 120 ° C. or less. The polyhydroxycarboxylic acid skeleton, the toner resin of claim 1 or 2, wherein the hydroxy carboxylic acid having 2 to 6 carbon atoms is obtained by (co) polymerization. The toner resin according to claim 3 , wherein the hydroxycarboxylic acid is lactic acid. The polyhydroxycarboxylic acid skeleton, toner resin according to any one of claims 1 to 4, characterized in that is obtained by ring-opening polymerization of lactide. 6. The toner resin according to claim 5 , wherein the lactide is a mixture of L-lactide and D-lactide. The resin for toner according to any one of claims 1 to 6, wherein the polyhydroxycarboxylic acid skeleton is a polylactic acid skeleton. In the polylactic acid resin composition having a polylactic acid skeleton, the following formula is represented by (II), the optical purity X (%) in the monomer component terms in claim 7, characterized in that is less than 80% The resin for toner described.
X (%) = | X (L-form) -X (D-form) | (II)
[However, in the formula (II), X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ] Toner characterized in that it is manufactured using a toner resin according to any one of claims 1-8. A developer comprising at least the toner according to claim 9 .

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