JP5509797B2 - Toner, developer using the toner, image forming method, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and a developer, an image forming method, an image forming apparatus, and a process cartridge using the toner. About.

  Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, and the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.

  The toner used for developing an electrostatic image is generally colored particles containing a colorant, a charge control agent, and the like in a binder resin. The production methods are roughly classified into a pulverization method and a polymerization method. is there.

  In the pulverization method, a toner composition is obtained by pulverizing and classifying a toner composition obtained by uniformly dispersing a colorant, a charge control agent, an offset preventing agent and the like in a thermoplastic resin by melt mixing. According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the toner composition obtained by melt mixing must be made sufficiently brittle. When pulverizing such a toner composition, particles having a wide particle size distribution are likely to be formed. At this time, in order to obtain a copy image with good resolution and gradation, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more must be removed by classification, yield. Is very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, etc. in the thermoplastic resin, and the fluidity, developability, durability, image quality, etc. of the obtained toner are adversely affected. There's a problem.

  Therefore, in Patent Documents 1 and 2, a resin solution in which a resin synthesized in advance by a polymerization reaction is dissolved is used as a dispersion (auxiliary) agent such as a surfactant or a water-soluble resin and a dispersion stabilizer such as inorganic fine particles and resin fine particles. There has been proposed a dissolved resin suspension method in which a toner is obtained by dispersing in an aqueous medium in the presence and removing the solvent by heating, decompression or the like. According to this dissolved resin suspension method, a uniform toner can be obtained without classification.

  In addition, in an electrophotographic image forming apparatus, releasability (hereinafter also referred to as offset resistance) to a heating member is required in a fixing process by a contact heating method performed using a heating member such as a heat roller. . This offset resistance is solved by using a modified polyester resin in the dissolved resin suspension method (see Patent Document 3).

  By the way, most of the binder resin occupying 70% or more of the constituent components of the toner is made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, large consumption of petroleum resources, and emission of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a plant that takes in carbon dioxide in the atmosphere and grows as a binder resin and uses this plant-derived resin, the resulting carbon dioxide only circulates in the environment, causing global warming problems and petroleum. There is a possibility that the problem of resource depletion can be solved simultaneously, and various toners using such plant-derived resins as binder resins have been proposed. For example, Patent Document 4 proposes using polylactic acid as a binder resin. However, when polylactic acid is used as it is as in this proposal, the concentration of the ester bond is higher than that of the polyester resin, so that the action as a thermoplastic resin is lowered during fixing. Further, since the toner becomes very hard, there is a problem that the grindability is poor and the productivity is inferior.

  Further, Patent Document 5 proposes an electrostatic charge image developing toner containing a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a tri- or higher functional oxycarboxylic acid, and a colorant. Yes. However, in this proposal, a polyester resin formed by a dehydration polycondensation reaction between a hydroxyl group of lactic acid and a carboxyl group of an oxycarboxylic acid having three or more functional groups is branched or networked, and is compared with a linear polyester resin. Solvent solubility is low. Further, since the sharp melt property is also impaired, there is a problem that the low temperature fixability is lacking.

  Further, Patent Document 6 discloses an electrophotographic toner containing a polylactic acid-based biodegradable resin and a terpene phenol copolymer in order to improve thermal characteristics. However, low temperature fixability and hot offset property are disclosed. Cannot be satisfied at the same time.

  Since the toners described in these documents are all obtained by a pulverization method, there is a problem of toner loss caused by classification and disposal associated therewith. Further, since the amount of energy required for the pulverization method is relatively large, further reduction of the environmental load is required.

  Moreover, polylactic acid which is widely available as a plant-derived resin is synthesized by dehydration condensation of lactic acid or ring-opening polymerization of lactic acid cyclic lactide as described in Patent Documents 7 and 8. For this reason, when manufacturing a toner using polylactic acid, the dissolution resin suspension method like patent documents 1-3 can be used. However, since polylactic acid has high crystallinity only in the L-form or D-form, the solubility in an organic solvent is extremely low, and it is difficult to use the dissolved resin suspension method. On the other hand, Patent Document 9 discloses that the L-form and D-form of polylactic acid are mixed to lower the crystallinity and improve the solubility in an organic solvent.

  However, since polylactic acid has a large number of polar groups per unit molecule, when a toner is produced using polylactic acid with reduced crystallinity, it is more affected by humidity than when the crystallinity is high. As a result, the toner heat-resistant storage stability deteriorates, the toner fluidity fluctuates due to moisture absorption, and the charge amount control becomes difficult. In particular, it is difficult to reduce the change in the charge amount between the low temperature and low humidity condition and the high temperature and high humidity condition. Therefore, there is a problem that the charge amount and the image density are not stable.

  On the other hand, in order to solve various problems in the heat-resistant storage stability and change in charge amount of the toner, various types of capsule-structured toners having core particles containing a binder resin and a shell layer covering the core particles have been proposed. This toner having a capsule structure has a structure in which the core portion is soft and inferior in heat-resistant storage stability and the charge amount is easily changed by the heat-resistant storage stability and charge stability of the shell portion.

  For example, in Patent Documents 10 to 14, a developer in which the surface of a toner binder resin is coated with an acrylic polymer or a styrene / acrylic copolymer is used. In Patent Documents 15 to 17, a polyester resin is coated on the surface of a toner binder resin. Coated developers have been proposed. However, although these developers can obtain excellent heat-resistant storage stability, the resin fine particles cover the surface of the toner binder resin, so that sufficient low-temperature fixability cannot be obtained. Further, there has been a problem that the resin fine particles on the surface are peeled off by long-term stirring in the developing unit, and the charge amount of the toner is changed with time.

  Patent Document 18 proposes a developer in which a surface of a toner binder resin is coated with a polyurethane resin. Since the polyurethane resin has excellent adhesion to various resins, it adheres firmly to the surface of the toner binder resin, and the resin particles on the surface do not peel off due to long-term stirring in the developing unit. Therefore, stable chargeability can be obtained. However, the polyurethane resin is advantageous in terms of protecting the toner base due to its high strength, but has a problem that the pressure required for fixing becomes high, which is disadvantageous for low-temperature fixing.

  In contrast, Patent Document 19 discloses a developer in which the surface of a toner binder resin is coated with a heat-dissociable urethane resin, and Patent Document 20 discloses a urethane in which a polyester having sharp melt properties is modified on the surface of a toner binder resin with urethane. Developers coated with modified polyester have been proposed. As a result, the toner can be stably charged with long-term agitation, and has improved heat-resistant storage stability and low-temperature fixability. However, in recent years, there is a high interest in energy saving of electrophotographic copying machines and printers, and further low-temperature fixing is desired. In Patent Documents 19 to 20, petroleum-based resins generally used in the conventional toner field such as styrene / acrylic resins and polyester resins are used as binder resins, and in order to obtain sufficient low-temperature fixability. There was a limit.

  Thus, a resin having a polyhydroxycarboxylic acid skeleton as well as low-temperature fixability, heat-resistant storage stability, hot offset resistance, charging stability in long-term stirring, high charging stability against changes in the usage environment such as temperature and humidity ( For example, a toner containing polylactic acid and related technology have not been obtained yet, and further improvement and development are desired at present.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention, even when using a resin having a polyhydroxycarboxylic acid skeleton (for example, polylactic acid), is excellent in low-temperature fixability while ensuring hot offset resistance and heat resistant storage stability, and can be used for long-term stirring. It is an object of the present invention to provide a toner having good charging stability against changes in the usage environment such as charging stability and temperature / humidity, and a developer, an image forming method, an image forming apparatus, and a process cartridge using the toner.

  As a result of intensive studies to achieve the above object, the inventors of the present invention are toners in which a resin made of a predetermined polymer is attached to the surface of a resin having a polyhydroxycarboxylic acid skeleton. It has been found that the above-mentioned problems can be solved by using a polyurethane-acrylic polymer composite resin as the polymer, and the present invention has been completed.

  Specifically, the toner according to the present invention and the developer, the image forming method, the image forming apparatus, and the process cartridge using the toner in order to solve the above problems are specifically described in the following (I) to (XIII). It has the following technical features.

(I): a toner including resin particles (C) having a first resin (a) and resin particles (B) containing a second resin (b), wherein the resin (a) is , polyurethane - is composed of an acrylic polymer composites, it is attached to the surface of the resin particles (B), the resin (b) is to have a non-crystalline polyhydroxycarboxylic acid skeleton, the resin (a) The toner is characterized in that the composition ratio of polyurethane and acrylic polymer contained in the toner is 2: 8 to 6: 4 .

(II): The resin (b) has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and an optical purity X (%) represented by the following formula (1) is 80% or less. The toner according to (I) above.
Optical purity X (%) = | X (L form) -X (D form) | ... Formula (1)
[However, X (L-form) represents the L-form ratio (mol%) contained in the resin (b) in terms of optically active monomer, and X (D-form) represents the resin (in terms of optically active monomer) ( The D-form ratio (mol%) contained in b) is represented. ]

(III): The toner according to the above (I) or (II), wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms. It is.

(IV): The toner according to any one of (I) to (III), wherein the resin (b) contains a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton. .

(V): The resin (b) is a linear chain obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than the polyester diol (b11) together with an extender. The toner according to any one of (I) to (IV) above, which comprises a polyester resin (b1) in the form of a powder.

(VI): The toner according to (V), wherein a mass ratio of the polyester diol (b11) to the polyester diol (b12) is 31:69 to 90:10.

(VII): The resin (b) contains the linear polyester resin (b1) and the resin (b2) obtained by reacting the precursor (b0) (V ) Or (VI).

(VIII): The toner according to any one of (V) to (VII), wherein the extender is diisocyanate or dicarboxylic acid .

(IV): A developer comprising the toner described in any one of (I) to (VIII) above.

(X): The developer described in (IX) above, further comprising a carrier.

(XI): An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of (I) to (VIII) above. A development process for forming a visible image by developing using the image, a transfer process for transferring the visible image to a recording medium, a fixing process for fixing the transfer image transferred to the recording medium to the recording medium, An image forming method characterized by comprising:

(XII): an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image as described in (I) to (VIII) above. A developing unit that develops a visible image by developing with the toner according to any one of the above, a transfer unit that transfers the visible image to a recording medium, and a transfer image that is transferred to the recording medium An image forming apparatus comprising: fixing means for fixing to a recording medium.

(XIII): an electrostatic latent image bearing member, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image bearing member, and the electrostatic latent image described above in (I) to (VIII) And a developing unit that forms a visible image by developing with the toner described in any one of the above, and is detachable from the main body of the image forming apparatus.

  According to the present invention, even when a resin having a polyhydroxycarboxylic acid skeleton (for example, polylactic acid) is used, it is excellent in low-temperature fixability while ensuring hot offset resistance and heat-resistant storage stability, and in long-term stirring. It is possible to provide a toner having good charging stability against changes in usage environment such as charging stability and temperature / humidity, and a developer, an image forming method, an image forming apparatus, and a process cartridge using the toner.

1 is a schematic explanatory diagram illustrating a configuration example in an embodiment of an image forming apparatus used in an image forming method according to the present invention. 1 is a schematic explanatory diagram illustrating a configuration example in an embodiment of a tandem color image forming apparatus used in an image forming method according to the present invention. FIG. 3 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 2. It is a schematic explanatory drawing which shows the structural example in one Embodiment of the process cartridge used by this invention.

(toner)
The toner according to the present invention is a toner including resin particles (C) having a first resin (a) and resin particles (B) containing a second resin (b), wherein the resin ( a) is composed of a polyurethane-acrylic polymer composite, is attached to the surface of the resin particles (B), and the resin (b) has an amorphous polyhydroxycarboxylic acid skeleton. To do. Further, it contains other components as required.

Next, the toner according to the present invention will be described in more detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.

<Resin particles (B) and second resin (b)>
The resin particles (B) contain the resin (b) that is the second resin, and contain other components as necessary.

  The shape, structure, and size of the resin particles (B) are not particularly limited as long as they contain the resin (b) and are in the form of particles. For example, the volume average particle diameter (Dv) of the resin particles (B) is such that the particle diameter ratio between the Dv of the resin particles (A) and the Dv of the resin particles (B) described later is easily obtained. Although 15 micrometers is preferable, More preferably, it is 0.5-10 micrometers, Most preferably, it is 1-8 micrometers, but this invention is not limited to this.

-Second resin (b)-
The second resin (b) is not particularly limited as long as it contains a polyhydroxycarboxylic acid skeleton, and is formed by polymerizing hydroxycarboxylic acid by various methods or having a polyhydroxycarboxylic acid skeleton. Examples thereof include those obtained by polymerizing the obtained cyclic ester as a starting material.

In the present invention, the second resin (b) has an amorphous polyhydroxycarboxylic acid skeleton.
Here, the non-crystalline property means that the temperature is raised from 20 ° C. to 250 ° C. at 10 ° C./min using a differential scanning calorimeter (DSC), then the temperature is lowered to 20 ° C. at 10 ° C./min, In the two temperature rising processes where the temperature is increased from 20 ° C. to 250 ° C. at a rate of 10 ° C./min, neither means a melting peak.
The non-crystalline property in the present invention is particularly preferably a product obtained by racemizing a resin having an L-form polyhydroxycarboxylic acid skeleton and a resin having a D-form polyhydroxycarboxylic acid skeleton. It has high transparency in the non-crystalline state, it can obtain high affinity with various colorants even though there are few functional groups such as organic acids and hydroxyl groups, and it has good solubility in solvents and is easy to handle. Excellent.

--Hydroxycarboxylic acid and cyclic ester--
Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), and mixtures thereof. It is done.

  The cyclic ester capable of forming a polyhydroxycarboxylic acid skeleton is not particularly limited as long as it can form a polyhydroxycarboxylic acid skeleton by ring-opening polymerization, and can be appropriately selected according to the purpose. Examples include lactide, D-lactide, DL-lactide, racemic lactide, glycolide, γ-butyrolactone, δ-valerolactone, 6-valerolactone, and ε-caprolactone. These may be used individually by 1 type and may use 2 or more types together.

  Among these, from the viewpoints of transparency and thermal characteristics of the resin particles (C) described later, the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid, more preferably 3 to 6 carbon atoms. Hydroxycarboxylic acid, particularly preferably glycolic acid, lactic acid, glycolide, and lactide, and particularly preferably glycolic acid, lactic acid, and lactide. When the carbon number is 2, the polyhydroxycarboxylic acid skeleton cannot have optical activity, and when the carbon number is 1 or less, the formation of the polyhydroxycarboxylic acid skeleton is substantially impossible. Further, when the number of carbon atoms is 7 or more, since many methylene chains are contained, the glass transition point (Tg) is lowered, and it may be difficult to use as a toner.

  The method for synthesizing the resin (b) is not particularly limited as long as a resin having a polyhydroxycarboxylic acid skeleton can be obtained from the above starting material. For example, a method of directly dehydrating and condensing a hydroxycarboxylic acid. And a method of ring-opening polymerization of the corresponding cyclic ester. Among these polymerization methods, ring-opening polymerization of a cyclic ester is preferable from the viewpoint of increasing the molecular weight of the polyhydroxycarboxylic acid to be polymerized. In addition, when synthesizing by ring-opening polymerization using a cyclic ester of hydroxycarboxylic acid as a starting material, the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by polymerizing the hydroxycarboxylic acid constituting the cyclic ester. For example, the polyhydroxycarboxylic acid skeleton of the resin (b) obtained using lactide is a skeleton obtained by polymerizing lactic acid. Further, a racemic amorphous resin can be obtained by using a proper amount of L-type and D-type monomers in combination. In the case of using lactide, L-type lactide and D-type lactide can be mixed and used. Alternatively, ring-opening polymerization of meso-type lactide or mixing of either D-type or L-type lactide and meso-type lactide. It can also be used.

  The monomer constituting the polyhydroxycarboxylic acid skeleton contained in the resin (b) has optical activity. The optical activity X (%) of the resin (b) represented by the following formula (1) is preferably 80% or less, more preferably 60% or less. Within this range, solvent solubility and resin transparency are improved.

Optical purity X (%) = | X (L-form) -X (D-form) | Formula (1)
[However, X (L form) represents the L form ratio (%) contained in the resin (b) in terms of optically active monomer, and X (D form) represents the resin (b) in terms of optically active monomer. Represents the D-form ratio (%) contained]

  When the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, particularly when only the polyester resin (b1) described later is used as the resin (b), the optical purity X (%) is 80% or less. It is preferable that there is, more preferably 60% or less. Within this range, the solvent solubility is improved and the production method (I) described later, which is a preferred production method, can be easily applied.

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

  When the resin (b) is used, it is easy to uniformly disperse the pigment and wax in the resin and the transparency is high. Therefore, when the resin (b) is used for a toner containing the pigment or wax, the image density and haze degree are used. Has a feature of improving.

--- Polyester resin (b1)-
The polyester resin (b1) contained in the resin (b) is not particularly limited as long as it is a polyester resin having a polyhydroxycarboxylic acid skeleton, and can be appropriately selected according to the purpose. The thing which has a branched chain is mentioned. Especially, it is preferable that it is a linear polyester-type resin (b1). The linear polyester resin (b1) is excellent in sharp melt properties and advantageous for low-temperature fixing. Moreover, compared with what has a branched chain, since the solubility to a solvent is good and the viscosity when melt | dissolving in a solvent is also low, handling property is good.

  The production method of the linear polyester-based resin (b1) is not particularly limited as long as a polyester-based resin having a polyhydroxycarboxylic acid skeleton is obtained, but the polyester diol (b11) having a polyhydroxycarboxylic acid skeleton; It is preferable to react polyester diol (b12) other than this polyester diol (b11) with an extender. Thereby, the physical properties of the toner can be freely controlled. In particular, the solvent solubility and storage stability of the resin can be improved, and the fixing temperature range can be widened.

--- Polyesterdiol (b11) ---
The polyester diol (b11) having a polyhydroxycarboxylic acid skeleton is not particularly limited as long as it is a polyester having a polyhydroxycarboxylic acid skeleton and a diol in the molecule. For example, the polyester diol (b11) was used for the polymerization of the resin (b). Along with the hydroxycarboxylic acid or cyclic ester, the diol (11) may be added and copolymerized. The diol (11) is not particularly limited as long as it has two hydroxyl groups in the molecule. For example, 1,3-propanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, 1,6-hexanediol, alkylene oxides of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (alkylene oxide is abbreviated as AO hereinafter), specific examples are ethylene oxide (hereinafter abbreviated as EO) ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) adduct (added mole number 2 to 30), and combinations thereof, preferably 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol An AO adduct of bisphenol A, more preferably, 1,3-propylene glycol and 1,3-propanediol.

--- Polyesterdiol (b12) ---
The polyester diol (b12) other than the polyester diol (b11) having a polyhydroxycarboxylic acid skeleton is not particularly limited as long as it is a polyester diol other than the polyester diol (b11), and can be appropriately selected according to the purpose. For example, the thing similar to the reaction material of diol (11) and dicarboxylic acid (13) can be used. That is, it can be obtained by adjusting the charge ratio of diol and dicarboxylic acid during polymerization to make the hydroxyl group excessive. Preferred examples of the polyester diol (b12) include 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S). AO (EO, PO, BO, etc.) adducts (addition mole number 2 to 30), and one or more selected from these combinations, terephthalic acid, isophthalic acid, adipic acid, succinic acid, and these It is a reaction product with one or more selected from the combined use.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyester diol (b11) and the polyester diol (b12) is 500 to 30, from the viewpoint of adjusting physical properties (for example, solubility and glass transition temperature) of the polyester resin (b1). 000 is preferable, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 5,000.

  The elongation agent used for the elongation of the polyester diol (b11) and the polyester diol (b12) has at least two functional groups capable of reacting with the hydroxyl groups contained in the polyester diol (b11) and the polyester diol (b12). Although it will not restrict | limit especially if it is a thing, A bifunctional thing is mentioned among dicarboxylic acid (13) and its anhydride, polyisocyanate (15), and polyepoxide (19). Of these, from the viewpoint of compatibility with the polyester diol (b11) and the polyester diol (b12), preferred are diisocyanate compounds and dicarboxylic acid compounds, and more preferred are diisocyanate compounds. Specifically, succinic acid, adipic acid, maleic acid (and anhydride), fumaric acid (and anhydride), phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4 '-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, etc., among which succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and anhydrous) Product), fumaric acid (and anhydride), HDI, and IPDI There, more preferably maleic acid (and anhydride), fumaric acid (and anhydride), as well as IPDI.

  The content of the extender in (b1) is preferably 0.1% by mass to 30% by mass and more preferably 1% by mass with respect to the polyester resin (b1) from the viewpoints of transparency and thermal characteristics. % To 20% by mass.

  The content of the linear polyester resin (b1) contained in the resin (b) may be appropriately adjusted according to the use, but is preferably from the viewpoint of transparency and thermal characteristics of the resin particles (C). Is 40% by mass to 100% by mass, and more preferably 60% by mass to 90% by mass with respect to the mass of the resin (b). If it is less than 40% by mass, the resin content may be too small to function as a toner. In particular, if it is less than 60% by mass, the resin content is small and the fixability, pigment dispersibility, and release agent dispersibility may be inferior. If it exceeds 90% by mass, pigment other than the resin, release agent, charge control A sufficient amount of the agent and the like cannot be contained, and the colorability, releasability and chargeability may be inferior. If the optical purity (X) in terms of monomer components of the hydroxycarboxylic acid constituting the polyester resin (b1) is 80% or less, from the viewpoint of solvent solubility, the polyester resin (b1) composed of an optically active monomer. ) In the resin (b) is preferably the same as described above. When the optical purity (X) exceeds 80% in terms of monomer component, from the viewpoint of solvent solubility, the content (Y (%)) of the polyester resin (b1) in the resin (b) is the optical purity X Therefore, it is preferable to satisfy Y ≦ −1.5X + 220. When this relationship is not satisfied, the solubility of the polyester resin (b1) in the solvent is significantly reduced.

  The mass ratio of the polyester diol (b11) having a polyhydroxycarboxylic acid skeleton constituting the linear polyester resin (b1) and the polyester diol (b12) other than the polyester diol (b11) is preferably 31:69 to 90:10, and more preferably 40:60 to 80:20 from the viewpoint of the transparency and thermal characteristics of the resin particles (C). When the mass ratio of the polyester diol (b11) is lower than 31:69, it may be disadvantageous in terms of low-temperature fixability, and when the mass ratio of the polyester diol (b11) is higher than 90:10, preservability, It may be disadvantageous in terms of environmental stability.

  The component other than the polyester resin (b1) contained in the resin (b) is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include various resins, and these various resins may be used in combination. .

-Resins other than polyester resin (b1) contained in resin (b)-
As the resin other than the polyester resin (b1) contained in the resin (b), any known resin may be used in combination with the polyester resin (b1). As the resin used in combination other than the polyester resin (b1), a preferable resin can be appropriately selected according to the use and purpose. In addition, the resin used in this manner may be a resin (b2) obtained by a reaction of a precursor (b0) described later in a resin particle forming step described later, from the viewpoint that particle formation is easy. A method of using the precursor (b0) and containing the resin to be used in combination is preferable. As the reaction method for obtaining the resin (b2) from the precursor (b0) and the precursor (b0), those described below can be used.

  Other than the polyester-based resin (b1), preferred as a resin to be used in combination is a vinyl resin, a polyester resin, a polyurethane resin, an epoxy resin, and a combination thereof, more preferably a polyurethane resin and a polyester resin. Particularly preferred are polyester resins and polyurethane resins containing 1,2-propylene glycol as a structural unit.

  As content of resin other than polyester-type resin (b1), what is necessary is just to adjust suitably according to a use, but from the viewpoint of transparency of a resin particle (C) and a thermal characteristic, with respect to the mass of resin (b). 0 mass%-60 mass% are preferable, More preferably, they are 10 mass%-40 mass%.

--Precursor (b0)-
The precursor (b0) in the present invention is not particularly limited as long as the resin (b2) can be obtained. For example, a prepolymer (α) having a reactive group (hereinafter referred to as “reactive group-containing prepolymer ( α) ”)) and a curing agent (β). Here, the “reactive group” refers to a group that can react with the curing agent (β). In this case, as a method of forming the resin particles (B) containing the resin (b2) obtained by reacting the precursor (b0) in the step of forming the resin particles (C), a reactive group-containing prepolymer (α ) And a curing agent (β) and, if necessary, an oil phase containing an organic solvent (u) is dispersed in the aqueous dispersion (W) of the resin particles (A), and the reactive group-containing prepolymer (α ) And a curing agent (β) are reacted to form resin particles (B) containing the resin (b2); a reactive group-containing prepolymer (α) or an organic solvent solution or dispersion thereof is added to resin particles ( A method of forming a resin particle (B) containing a resin (b2) by dispersing it in an aqueous dispersion (W) of A) and adding a water-soluble curing agent (β) to this to react; a reactive group When the containing prepolymer (α) is cured by reacting with water, Resin particles (B2) containing resin (b2) are reacted with water by dispersing the group-containing prepolymer (α) or an organic solvent solution or dispersion thereof in an aqueous dispersion (W) of resin particles (A). ) Can be exemplified.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following combinations [1] and [2].
Combination [1] The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). There is a combination.
Combination [2] The reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. There is a combination.

-Reactive group-containing prepolymer (α) and curing agent (β)-
Among these, the combination of [1] is preferable from the viewpoint of the reaction rate in water. In the above combination [1], as the functional group (α1) capable of reacting with the active hydrogen compound, an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, preferred are an isocyanate group (α1a), a blocked isocyanate group (α1b), and an epoxy group (α1c), and more preferred are an isocyanate group (α1a) and a blocked isocyanate group (α1b).

  The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; Etc.]: C1-20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, -cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] ]; Basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]: and mixtures of two or more thereofOf these, oximes are preferred, and methyl ethyl ketoxime is more preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, polyester (αx), epoxy resin (αy), and polyurethane (αz) are preferable, and polyester (αx) and polyurethane (αz) are more preferable.

  Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide and polytetramethylene oxide. Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ε-caprolactone ring-opening polymer), and the like. Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin. Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

  The following [1] and [2] may be mentioned as a method for incorporating a reactive group into polyester (αx), epoxy resin (αy), polyurethane (αz), and the like.

Method [1] A method in which one of two or more components is excessively used to leave the functional group of the component at the end. Method [2] One of two or more components is excessively used. A method in which a functional group of a constituent component is left at the end by using the compound, and a compound containing a functional group and a reactive group capable of reacting with the remaining functional group is reacted.

  In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / hydroxyl group [OH] to carboxyl group [COOH]. [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.

  In the method [2], an isocyanate group-containing prepolymer is obtained by reacting the prepolymer obtained in the method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to react with a blocked isocyanate group. A prepolymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride. The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate so that the ratio of polyisocyanate is isocyanate group [NCO] and hydroxyl group. The equivalent ratio [NCO] / [OH] of the containing polyester to the hydroxyl group [OH] is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1 on average. .8 to 2.5. By setting it in the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) is increased, which is preferable in terms of hot offset resistance. The number average molecular weight (Mn) of the reactive group-containing prepolymer (α) is not particularly limited, but is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably. Is 2,000 to 10,000. When Mn is less than 500, the resin (b2) cannot obtain a sufficient molecular weight and lacks hot offset resistance, and when it exceeds 30,000, the softening temperature of the resin (b2) increases, and the low-temperature fixability point. Is disadvantageous. The weight average molecular weight (Mw) of the reactive group-containing prepolymer (α) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, Especially preferably, it is 4,000-20,000. When Mw is less than 1,000, the resin (b2) does not have a sufficient molecular weight and lacks hot offset resistance, and when it exceeds 50,000, the softening temperature of the resin (b2) increases and low temperature fixability. This is disadvantageous. The viscosity of the reactive group-containing prepolymer (α) is not particularly limited, but is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. Setting it to 2,000 poise or less is preferable in that resin particles (C) having a sharp particle size distribution can be obtained with a small amount of an organic solvent.

  In the present invention, the curing agent (β) is not particularly limited as long as it reacts with the reactive group-containing prepolymer (α) to give the resin (b2). As described above, the active hydrogen group-containing compound Examples thereof include (β1) and a compound (β2) capable of reacting with an active hydrogen-containing group.

  Examples of the active hydrogen group-containing compound (β1) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, preferred are polyamine (β1a), polyol (β1b) and water (β1d), more preferred are polyamine (β1a) and water (β1d), and particularly preferred are blocked. Polyamines and water (β1d).

As the polyamine (β1a), aliphatic polyamines (C2 to Cl8): [1] aliphatic polyamine {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), Polyalkylene (C2 to C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]}; [2] these alkyls (C1 to C4) Or substituted hydroxyalkyl (C2-C4) [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethy Diamine, methyliminobispropylamine, etc.]; [3] Alicyclic or heterocyclic aliphatic polyamine [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5 ] [4] Aromatic ring-containing aliphatic amines (C8-C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4-C15): 1,3-diamino Heterocyclic polyamines (C4 to C15) such as cyclohexaneisophoronediamine, mensendiamine, 4,4′-methylenedicyclohexanediamine (hydrogenated methylenedianiline): piperazine, N-aminoethylbiperazine, 1,4- Diaminoethylbiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine, and aromatic poly Mines (C6-C20): [1] Unsubstituted aromatic polyamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethane Diamine (polyphenyl polymethylene polyamine), diaminodiphenyl sulfone, benzidine, thiodianiline, bis (3,4-diaminophenol) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ′, 4 ″ -triamine, naphthylenediamine, etc .; [2] aromatic polyamines having a nucleus-substituted alkyl group [C1-C4 alkyl groups such as methyl, ethyl, n- and i-propylbutyl], such as 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4 '-Diamino-3,3'-dimethyldiphenylmethane,4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2 , 6-diaminobenzene, 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1 , 4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 3,3,5,5-tetramethylbenzidine, 3,3,5,5-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3′-methyl-2 ′, 4-diaminodiphenylmethane, 3,3′-diethyl-2,2′-diaminodiphenylmethane, 4,4-di Amino-3,3′-dimethyldiphenylmethane, 3,3,5,5-tetraethyl-4,4-diaminobenzophenone, 3,3,5,5-tetraethyl-4,4′-diaminodiphenyl ether, 3,3,5 , 5-tetraisopropyl-4,4′-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions: [3] nuclear substituted electron withdrawing groups (halogens such as Cl, Br, I, F; methoxy; An aromatic polyamine having an alkoxy group such as ethoxy: nitro group, etc. [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4- Chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro- , 3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3,3-dichlorobenzidine, 3,3-dimethoxy Benzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane Bis (4-aminophenyl) sulfide bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4-methylenebis (2-iodoaniline) 4,4-methylenebis (2-bromoaniline), 4,4-methylenebis (2-fur Oroanirin), 4-aminophenyl-2-chloroaniline, etc.]; [4] aromatic polyamine having a secondary amino group [the above-mentioned [1] to some or all -NH ₂ aromatic polyamines (3) are —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4 -Aminobenzene, etc.], polyamide polyamines: low molecular weight polyamides obtained by condensation of dicarboxylic acids (such as dimer acids) and excess (more than 2 moles per mole of acid) polyamines (such as alkylene diamines, polyalkylene polyamines, etc.) Polyamines and other polyether polyamines: Polyether polyols (polyalkylene glycols, etc.) cyanoethylated products And hydrides thereof. Of these, 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof are preferable as the polyamine (β1a).

  Examples of polyamines in which polyamine (β1a) is blocked with a detachable compound include ketimines obtained from the polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Examples thereof include aldimine compounds, enamine compounds, and oxazolidine compounds obtained from compounds and aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde).

  Examples of the polyol (β1b) include diols and polyols. Examples of the diol include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol. , Dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene) Glycol, polytetramethylene ether glycol, etc.); C4-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene glycol Or AO [EO, PO, BO, etc.] adducts of alicyclic diol (addition mole number 1 to 120); AO (AO, PO, BO, etc.) addition of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Products (number of added moles 2 to 30); polylactone diol (poly ε-caprolactone diol and the like); and polybutadiene diol and the like. Examples of the polyol include 3 to 8 or more polyhydric aliphatic alcohols having 3 to 36 carbon atoms (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, Sorbitol, sorbitan, and polyglycerin; saccharides and derivatives thereof such as sucrose and methyl glucoside); AO adducts of polyhydric aliphatic alcohols (addition mole number: 2 to 120); trisphenols (such as trisphenol PA) AO adduct (addition mole number 2-30); AO adduct (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl monomers Copolymer, etc.]; It is. Of these, diol alone or a mixture of diol and a small amount of polyol is preferable.

  Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

  If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). The resin (b2) can be adjusted to a predetermined molecular weight by using the reaction terminator (βs) in combination with the active hydrogen group-containing compound (βl) at a certain ratio. As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.); monool (methanol, ethanol, isopropanol, butanol) , Phenol, etc.); monomercaptan (such as butyl mercaptan, lauryl mercaptan); monoisocyanate (such as lauryl isocyanate phenyl isocyanate); monoepoxide (such as butyl glycidyl ether).

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Among these, preferred are an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), and an organic group (α2e) blocked with a compound capable of removing the amino group, and more preferred. The thing is a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b). Examples of the organic group blocked with the compound from which the amino group can be removed include those similar to the case of the polyamine (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), and polyacid halide (β2e). Can be mentioned. Of these, preferred are polyisocyanate (β2a) and polyepoxide (β2b), and more preferred is polyisocyanate (β2a).

  The polyisocyanate (β2a) is an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, an alicyclic ring having 4 to 15 carbon atoms. Formula polyisocyanate, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, Oxazolidone group-containing modified products) and mixtures of two or more thereof. Among these, preferred are aromatic polyisocyanates having 6 to 15 carbon atoms, aliphatic polyisocyanates having 4 to 12 carbon atoms and alicyclic polyisocyanates having 4 to 15 carbon atoms.

  Examples of the polyepoxide (β2b) include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds, and aliphatic polyepoxy compounds. Among these, an aromatic polyepoxy compound and an aliphatic polyepoxy compound are preferable.

  Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2), dicarboxylic acid (β2c-1) alone, and dicarboxylic acid (β2c-1) And a small amount of a trivalent or higher polycarboxylic acid (β2c-2). Examples of the dicarboxylic acid (β2c-1) include alkanedicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenylsuccinic acid (dodecenylsuccinic acid). Acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.); C6-C40 alicyclic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.]; C4-C36 alkene dicarboxylic acid (Maleic acid, fumaric acid, citraconic acid, etc.); C8-36 aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) and the like. Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. Examples of the polycarboxylic acid (β2c-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).

Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride.
Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide acid iodide) of the above (β2c). Further, if necessary, the above-mentioned reaction terminator (βs) can be used together with the compound (β2) capable of reacting with the active hydrogen-containing group.

  In the above methods [1] and [2], the ratio of the curing agent (β) to be used is the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) and the curing agent (β The ratio [α] / [β] of the equivalent of the active hydrogen-containing group [β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, particularly preferably Is 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is handled as a divalent active hydrogen compound.

  A resin (b2) obtained by reacting a precursor (b0) containing a reactive group-containing prepolymer (α) and a curing agent (β) in an aqueous medium constitutes resin particles (B) and resin particles (C). Become an ingredient. The weight average molecular weight (Mw) of the resin (b2) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is not particularly limited, but is low temperature fixability and hot offset resistance. And preferably 3,000 or more, more preferably 3,000 to 10,000,000, and particularly preferably 5,000 to 1,000,000. If Mw is less than 3,000, the hot offset resistance is insufficient, and if it exceeds 1,000,000, it is disadvantageous in terms of low-temperature fixability.

  Further, during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) in the aqueous medium, the reactive group-containing prepolymer (α) such as a linear polyester resin (b1) and the curing The resin (b) contains a reactive group-containing prepolymer (α) and a curing agent (β) in an aqueous medium by incorporating a polymer that does not react with the agent (β), so-called [dead polymer], into the system. It becomes a mixture of the resin (b2) obtained by the reaction and a non-reacted resin such as the linear polyester-based resin (b1).

  The amount of the aqueous dispersion (W) used with respect to 100 parts by mass of the resin (b) is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass. If it is 50 parts by mass or more, the dispersed state of (b) is good, and if it is 2,000 parts by mass or less, it is economical.

  The physical properties of the resin (b) are not particularly limited as long as they have a polyhydroxycarboxylic acid skeleton, and may be appropriately selected depending on the application. Such physical properties include, for example, number average molecular weight (Mn) (measured by gel permeation chromatography), weight average molecular weight (hereinafter abbreviated as Mw), melting point (differential scanning calorimeter (DSC)). Measurement), glass transition point (hereinafter abbreviated as Tg), sp value (the calculation method of sp value is based on Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). It is done.

  Especially, as Mn of resin (b), Preferably it is 1,000-5,000,000, More preferably, it is 2,000-500,000. The Mw of the resin (b) is preferably 3,000 to 7,000,000, and more preferably 5,000 to 600,000. The melting point of the resin (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of the resin (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 200 ° C. The sp value of the resin (b) is preferably 8 to 16, more preferably 9 to 14.

  In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of each resin such as polyester resin other than polyurethane resin are determined by gel permeation chromatography (GPC) for tetrahydrofuran (THF) soluble matter. It is obtained under the following conditions.

Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Solution injection amount: 100 μL
Flow rate: 1 mL / min Measurement temperature: 40 ° C
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000)

  Moreover, Mn and Mw of a polyurethane resin are calculated | required on condition of the following using GPC.

Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μL
Flow rate: 1 mL / min Temperature: 40 ° C
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000)

  Melting | fusing point and Tg in this invention are calculated | required from DSC measurement or a flow tester measurement (when it cannot measure with DSC).

  When measuring by DSC, it measures by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Shimadzu Corporation DSC-60.

  For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.

(Flow tester measurement conditions)
Load: 30 kg / cm ²
Temperature increase rate: 3.0 ° C./min Die diameter: 0.50 mm
Die length: 10.0mm

<First resin (a); resin particles (A) and coating (P)>
The toner according to the present invention has a first resin (a), the first resin (a) is attached to the surface of the resin particles (B), and the first resin (a) is polyurethane As long as it is made of an acrylic polymer, its shape, structure, and size are not limited, and may be appropriately selected according to the purpose. However, the resin particles (A) or the coating particles (P) are coated with resin particles (A). It is preferably present on the surface of B). When the resin (a) is present as the resin particles (A) on the surface of the resin particles (B), it may be in the form of particles, and when it is present as the coating (P), it may be in the form of a film. That's fine. In the toner according to the present invention, whether the first resin (a) exists as the resin particles (A) or the coating (P) depends on the Tg and volume average particle diameter of the first resin (a). Depending on the production conditions (desolvation temperature, etc.) of the resin particles (C).

-Resin particles (A)-
The resin (a) attached to the surface of the resin particles (B) can be formed using a known polymerization method, and is preferably obtained as the resin particles (A). This is because the resin particles can easily adhere to the surface of the resin particles (B).

  The resin particles (A) in the present invention are considered to be bonded to the surface portion when an organic solvent and an active hydrogen-containing compound (amines) are dispersed in an aqueous medium to form organic dispersed fine particles. It is considered that the toner particles obtained as a result are unevenly distributed mainly on the surface portion.

  The particle size of the resin particles (A) is usually smaller than the particle size of the formed resin particles (B), and from the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of the resin particles (A) The value of (Dv)] / [volume average particle diameter (Dv) of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. If the particle size ratio exceeds 0.3, the resin particles (A) are not efficiently adsorbed on the surface of the resin particles (B), so that the particle size distribution of the obtained resin particles (C) becomes wide, and the heat resistance of the toner Preservability may deteriorate. On the other hand, when the particle size ratio is less than 0.001, productivity is deteriorated.

  The volume average particle diameter (Dv) of the resin particles (A) is appropriately adjusted within the above range of particle diameter ratio so as to be a particle diameter suitable for obtaining resin particles (C) having a desired particle diameter described later. can do. In general, the volume average particle diameter (Dv) of the resin particles (A) is preferably 0.005 to 1 μm. The upper limit is more preferably 0.75 μm, particularly preferably 0.6 μm, and the lower limit is more preferably 0.01 μm, particularly preferably 0.02 μm, and even more preferably 0.04 μm. However, for example, when it is desired to obtain resin particles (C) having a volume average particle diameter of 1 μm, the volume average particle diameter (Dv) of the resin particles (A) is preferably 0.005 to 0.30 μm, more preferably. When it is desired to obtain resin particles (C) having a volume average particle diameter of 10 μm in the range of 0.01 to 0.2 μm, the volume average particle diameter (Dv) of the resin particles (A) is preferably 0.05. It is -0.8 micrometer, More preferably, it is 0.1-1 micrometer. The volume average particle size is determined by laser type particle size distribution analyzer LA-920 (manufactured by Horiba), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, and the like. Can be measured. When there is a difference in the measured value of the particle diameter between the measuring devices, the measured value by ELS-800 is adopted.

  The resin (a) can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of the resin particles (A). This is because the toner of the present invention can be produced by using a dissolution suspension method, so that if the resin particles (A) are aqueous dispersions, they are uniformly dispersed even when added directly to an aqueous phase or emulsion. This is because it tends to adhere uniformly to the surface of the resin particles (B).

  The characteristics of the resin particles (A) are not particularly limited as long as the above-described purpose can be achieved, and among them, the resin particles (A) can be dissolved in water or a solvent used during dispersion. From the viewpoint of reducing swelling or the like, the molecular weight of the resin (a), sp value (the calculation method of the sp value is based on Polymer Engineering and Science, February, 1974, VoL14, No. 2P, 147 to 154), crystal It is preferable to appropriately adjust the properties, the molecular weight between crosslink points, and the like.

  Although there is no restriction | limiting in particular as a glass transition point (Tg) of resin (a), It is preferable that it is 40 to 100 degreeC, More preferably, it is 50 to 90 degreeC, Most preferably, it is 58 to 75 degreeC. ° C. Moreover, there is no restriction | limiting in particular as a weight average molecular weight of resin (a), However, It is preferable to set it as 9,000-200,000. When the Tg is less than 40 ° C. and / or the weight average molecular weight is less than 9,000, the storage stability of the toner deteriorates, and blocking may occur during storage and in the developing machine. On the other hand, when Tg exceeds 100 ° C. and / or the weight average molecular weight exceeds 200,000, the resin particles containing the resin (a) inhibit the adhesiveness to the fixing paper, and increase in the minimum fixing temperature is observed. May be. In addition, if the Tg of the resin (a) is lower than the temperature at which the aqueous resin dispersion is prepared, the effect of preventing coalescence of the resin particles (C) and prevention of fragmentation is reduced, and the particle size uniformity There is a possibility that the effect of increasing the heat resistance will be reduced and the heat-resistant storage stability of the toner will deteriorate. In addition, Tg in this invention is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure with DSC) as above-mentioned.

  When adjusting the glass transition point (Tg) of the resin (a), it can be easily adjusted by changing the molecular weight of the resin (a) and / or the monomer composition constituting the resin (a). As a method for adjusting the molecular weight of the resin (a) (the higher the molecular weight, the higher the temperature), a known method may be used. For example, in the case of polymerization by sequential reaction, the monomer charge ratio Adjustment.

  The aqueous dispersion of the resin (a) used in the present invention is produced by first polymerizing an aqueous polyurethane resin and then polymerizing an acrylic monomer in the presence of the aqueous resin.

The method for producing the aqueous polyurethane resin in the present invention is as follows. First, a prepolymer is prepared by a urethanization reaction in an organic solvent of a diisocyanate compound, a diol compound, a diol compound having a carboxyl group, and a hydroxyl compound having a polymerizable unsaturated group. Thereafter, the obtained NCO-terminated prepolymer is neutralized with a neutralizing agent such as a tertiary amine. Subsequently, (1) the polyfunctional carboxylic acid polyhydrazide compound is reacted with the terminal NCO group of the prepolymer, or (2) the chain is extended with a polyfunctional amine and / or polyfunctional carboxylic acid polyhydrazide, The NCO end group to be reacted with a polyfunctional carboxylic acid polyhydrazide is converted into an aqueous polyurethane resin having a —CONHNH ₂ group at the end. Thereby, it becomes a polyurethane aqueous dispersion.

  As the diisocyanate compound to be used, various known diisocyanates of aromatic, aliphatic or alicyclic can be mentioned. Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate. Aromatic diisocyanates such as 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-dicyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate, Examples include aliphatic or alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate and isophorone diisocyanate.

  Diols include (a) polyethers such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, (b) ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, etc. Dehydration condensation reaction of polyhydric alcohols with polyhydric carboxylic acids such as maleic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or caprolactone Polyester obtained by ring-opening polymerization reaction of cyclic ester, (c) Polydiol such as polycarbonate, (d) Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propyl Pyrene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, ethylene oxide or propylene oxide adduct of bisphenol A, ethylene oxide of bisphenol S And low molecular glycols such as Examples of the acid group-containing glycols that are water-solubilizing components include 2,2-dimethylolpropionic acid, 2,2-dimethylollacric acid, 2,2-dimethylolvaleric acid and other diols containing a carboxyl group in the molecule. Can be mentioned. Examples of the hydroxyl compound containing a polymerizable unsaturated group include β-hydroxyethyl methacrylate (HEMA), β-hydroxyethyl acrylate, γ-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, glycerin monoallyl ether, and the like. These diols may be used individually by 1 type, and may use 2 or more types together.

  The aqueous polyurethane resin of the present invention preferably has an aromatic ring or a nucleus-substituted aromatic ring unit derived from a polyol component. This improves the heat resistant storage stability of the resin and the adhesion to the toner binder resin.

  In order to introduce these aromatic rings and nucleus-substituted aromatic ring units into a polyurethane polymer, a copolymer comprising ethylene glycol (EG), neopentyl glycol (NPG), terephthalic acid (TPA) and isophthalic acid (IPA). Polyester can be used.

  A polyfunctional carboxylic acid polyhydrazide can be used as the end-capping agent to be reacted with the remaining NCO end group. Specific examples of the polyfunctional carboxylic acid polyhydrazide include oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide (ADH), sebacic acid dihydrazide, dodecanedioic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, Itaconic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 4,4′-oxybisbenzenesulfonyl hydrazide, trimesic acid trihydrazide, 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH), enocosan 2 Acid dihydrazide, 7,11-octadecadien-1,18-dicarbohydrazide, polyacrylic acid hydrazide, acrylamide-acrylic acid hydrazide copolymer, and the like. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide and 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH) are preferably used.

  Subsequently, an acrylic monomer is polymerized in the presence of the aqueous polyurethane dispersion produced by the above-described method to produce an aqueous dispersion of a polyurethane-acrylic polymer composite. Examples of acrylic monomers used include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid. Examples of the monomer mixture include methacrylic acid esters such as hexyl acid and glycidyl methacrylate, and styrene. Examples of polymerizable unsaturated monomers containing aldehyde groups or ketone groups include acrolein, diacetone acrylamide (DAAM), acetoacetoxyethyl methacrylate, p-formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone. , Vinyl acetophenone and vinyl benzophenone. Among these, diacetone acrylamide, acrolein, and vinyl methyl ketone are preferable.

  The composition ratio of the polyurethane and the acrylic polymer in the resin (a) is preferably 2: 8 to 6: 4, more preferably 3: 7 to 5: 5. If the polyurethane component is reduced from a composition ratio of 2: 8, the resin (a) becomes soft and heat resistant storage stability deteriorates, or the adhesion of the resin (a) to the toner surface decreases. It may peel off and it may be difficult to obtain a stable charge amount. Further, when the polyurethane component is increased more than the composition ratio 6: 4, the resin (a) becomes hard and the minimum fixing temperature may be increased, the resin (a) becomes weak against humidity, the heat resistant storage stability is deteriorated, and the environment changes. Sexual deterioration may be seen.

<Resin particles (C)>
In the toner according to the present invention, if the resin particles (C) are formed by adhering the first resin (a) to the surface of the resin particles (B) containing the second resin (b), The production method is not particularly limited.

  As a method for producing resin particles (C), any method and process may be used as long as the above conditions are satisfied. Manufacturing method (I) or (II) is mentioned.

  Production method (I): aqueous dispersion (W) of resin particles (A) containing resin (a), [resin (b) or an organic solvent solution or dispersion thereof (hereinafter referred to as (O1)), Or, [Resin (b) precursor (b0) or organic solvent solution or dispersion thereof] (hereinafter referred to as (O2)) is mixed, and (O1) or (O2) is added to the aqueous dispersion (W). In the case of the precursor (b0), the precursor (b0) is reacted to form the resin (b2), and the resin particles (B) containing the resin (b) in the aqueous dispersion (W) are formed. How to form. In this case, resin (a) (for example, resin particle (A) or coating (P)) adheres to the surface of resin particle (B) simultaneously with granulation of resin particle (B), and resin particle (C) An aqueous dispersion (X) is prepared from which an aqueous medium is removed.

  Production method (II): A method of producing resin particles (C) by coating resin particles (B) containing a resin (b) prepared in advance with a coating agent (W ′) containing a resin (a). In this case, the coating agent (W ′) may be liquid, solid, or any form, and after coating with the precursor (a ′) of the resin (a), the precursor (a ′) is reacted. The resin (a) may be used. The resin particles (B) to be used may be resin particles produced by an emulsion polymerization aggregation method, resin particles produced by a pulverization method, or any production method. It doesn't matter. Moreover, there is no limitation in the coating method using a coating agent (W '), For example, the resin particle (B) produced beforehand in the aqueous dispersion (W) of the resin particle (A) containing resin (a) ) Or a dispersion of the resin particles (B), a method of applying a solution of the resin (a) to the resin particles (B) as a coating agent, and the like.

  Especially, the manufacturing method of the said manufacturing method (I) is preferable at the point which can adhere a resin particle (A) to the surface of a resin particle (B) more firmly. Further, in the production method (I), the resin particles (A) are adsorbed on the surface of the resin particles (B) to prevent the resin particles (C) from being united with each other. (C) makes it difficult to be split. Thereby, the particle size distribution of the resin particles (C) is narrowed, the uniformity of the particle size is improved, and the effect of making uniform particles is exhibited.

  The resin particles (A) have (i) strength not to be destroyed by shearing at the temperature at which they are dispersed, (ii) they are difficult to dissolve or swell in water, (iii) resin (b) ) Or an organic solvent solution or dispersion thereof, or a resin (b) and a precursor (b0) or an organic solvent solution or dispersion thereof.

  Other components such as a charge control agent, a deforming agent, and a colorant, which will be described later, which are toner components may be included in the resin particles (B). For this reason, before mixing the aqueous dispersion (W) and (O) (O1 or O2), these charge control agents, deforming agents, colorants, etc. are dispersed in the solution (O). Also good. The charge control agent may be included in the resin particles (B) or externally added. When encapsulating, it may be dispersed in the solution of (O) like the colorant or the like, and when externally added, it may be externally added after the formation of the resin particles (C).

  In the method for producing resin particles (C), in the aqueous dispersion (W) of the resin particles (A), in addition to water, an organic solvent (acetone, methyl ethyl ketone) that is miscible with water among the organic solvents (u) described later. Etc. may be contained. As the organic solvent having this miscibility, those that do not cause aggregation of the resin particles (A), those that do not dissolve the resin particles (A), and those that do not hinder the granulation of the resin particles (C). There is no particular limitation, and the same applies to the content of the miscible organic solvent. For example, what does not remain in the resin particle (C) after drying using 40 mass% or less of the total amount with water is preferable.

-Organic solvent (u)-
For the preparation of the resin particles (C), an organic solvent (u) may be used for the purpose of dissolving / dispersing the constituent components of the resin particles (C). The organic solvent (u) may be added to the aqueous medium as needed during emulsification and dispersion in the dispersion to be emulsified [the oil phase (O1) containing the resin (b) or the resin (b), (b0). In the oil phase (O2) containing]. Specific examples of the organic solvent (u) include the following.

・ Aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetralin ・ Aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane and mineral spirit cyclohexane ・ Methyl chloride and methyl bromide methyl iodide Halogen solvents such as methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate ethyl cellosolve acetate, diethyl ether, tetrahydrofuran dioxane Ether solvents such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, Ketone solvents such as clohexanone, alcohol solvents such as methanol ethanol n-propanolisopropanol, n-butanol, isobutanol t-butanol, 2-ethylhexyl alcohol benzyl alcohol, amide solvents such as dimethylformamide dimethylacetamide, dimethyl sulfoxide, etc. Sulfoxide solvents, heterocyclic solvents such as N-methylpyrrolidone, mixed solvents of two or more of those listed above

-Plasticizer (v)-
For the preparation of the resin particles (C), a plasticizer (v) may be used for the purpose of plasticizing the resin to lower the lower limit of fixing, or for improving the solubility of the resin in a solvent. . The plasticizer (v) may be added to the aqueous medium as needed during emulsification and dispersion in the emulsified dispersion [the oil phase (O1) containing the resin (b) or the resins (b) and (b0). In the oil phase (O2) containing]. The plasticizer (v) is not particularly limited as long as it satisfies the above-mentioned purpose, and the following are exemplified.

(V1) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate diisodecyl, etc.]
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.]
(V3) Trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.]
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.]
(V5) Fatty acid ester [butyl oleate, etc.]
(V6) and mixtures of two or more thereof

-Emulsifier or dispersant-
For the preparation of the resin particles (C), an emulsifier or a dispersant may be used for the purpose of emulsifying / dispersing the constituent components. As the emulsifier or dispersant, a known surfactant (s), water-soluble polymer (t), or the like can be used. Moreover, said organic solvent (u), a plasticizer (v), etc. can be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

--Surfactant (s)-
For the preparation of the resin particles (C), a surfactant (s) may be used for the purpose of emulsifying / dispersing the constituent components. There is no restriction | limiting in particular as surfactant (s), Anionic surfactant (s-1), Cationic surfactant (s-2), Amphoteric surfactant (s-3), Nonionic surfactant ( s-4). The surfactant (s) may be used alone or in combination of two or more surfactants. Specific examples of (s) include those described in Patent Document 2 in addition to those described below.

--- Anionic surfactant (s-1) ---
As the anionic surfactant (s-1), carboxylic acid or a salt thereof, a sulfate ester salt, a salt of carboxymethylated product, a sulfonate salt, a phosphate ester salt, or the like is used.

  As the carboxylic acid of an anionic surfactant (s-1) or a salt thereof, a saturated or unsaturated fatty acid having 8 to 22 carbon atoms or a salt thereof can be used, for example, cabric acid, lauric acid, myristic acid, palmitic acid, Examples thereof include a mixture of stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid and ricinoleic acid, and higher fatty acids obtained by saponifying coconut oil, palm kernel oil, rice bran oil, beef tallow and the like. Examples of the salt of the carboxylate include salts such as sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, and alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.). Can be mentioned.

  As the sulfate ester salt of the anionic surfactant (s-1), a higher alcohol sulfate salt (sulfate ester of an aliphatic alcohol having 8 to 18 carbon atoms), a higher alkyl ether sulfate ester salt (having 8 to 18 carbon atoms). Sulfuric acid ester salt of EO or PO 1-10 mol adduct of aliphatic alcohol), sulfated oil (natural unsaturated oil or fat having 12 to 50 carbon atoms, or neutralized by neutralization by sulfation as it is), sulfuric acid Fatty acid esters (sulfurized and neutralized lower alcohol (carbon number 1-8) esters of unsaturated fatty acids (carbon numbers 6-40)) and sulfated olefins (sulfated olefins having 12-18 carbon atoms) Neutralized) can be used. Examples of the sulfate ester salt include sodium salt, potassium salt, amine salt, ammonium salt, quaternary ammonium salt, alkanolamine salt (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like. Examples of the higher alcohol sulfate ester salt include octyl alcohol sulfate ester salt, decyl alcohol sulfate ester salt, lauryl alcohol sulfate ester salt, stearyl alcohol sulfate ester salt, and alcohol synthesized using a Ziegler catalyst (for example, trade name: ALFOL1214). : Manufactured by CONDEA) and alcohol synthesized by the oxo method (for example, trade names: Dovanol 23, 25, 45, Diadol 115, 115H, 135: manufactured by Mitsubishi Chemical Corporation, trade name: tridecanol: Kyowa Hakko) Manufactured by the trade name: Oxocol 1213, 1215, 1415: manufactured by Nissan Chemical Co., Ltd.). Examples of the higher alkyl ether sulfate ester salt include lauryl alcohol EO 2 mol adduct sulfate ester salt and octyl alcohol EO 3 mol adduct sulfate ester salt. Examples of the sulfated oil include a salt of sulfate such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow and sheep fat. Examples of sulfated fatty acid esters include sulfate salts such as butyl oleate and butyl ricinoleate. Examples of the sulfated olefin include trade name: TEPOL (manufactured by Shell).

  Examples of the carboxymethylated salt include a carboxymethylated salt of an aliphatic alcohol having 8 to 16 carbon atoms, an EO of an aliphatic alcohol having 8 to 16 carbon atoms, or a carboxymethylated salt of an adduct having 1 to 10 moles of PO. Can be used. Examples of the salt of the carboxymethylated product of the aliphatic alcohol include octyl alcohol carboxymethyl sodium salt, lauryl alcohol carboxymethyl sodium salt, carboxymethyl sodium salt of dovanol 23, tridecanol carboxymethyl sodium salt and the like. It is done. Examples of salts of carboxymethylated products of EO or PO1-10 mol adducts of aliphatic alcohols include, for example, octyl alcohol EO or PO3 mol adduct carboxymethylated sodium salt, lauryl alcohol EO or PO4 mol adduct carboxymethylated sodium salt , And tridecanol EO or PO5 molar adduct carboxymethylated sodium salt.

  As the sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester salt, igepon T-type, and sulfonates of other aromatic ring-containing compounds can be used. Examples of the alkylbenzene sulfonate include sodium dodecylbenzenesulfonate. Examples of the alkyl naphthalene sulfonate include sodium dodecyl naphthalene sulfonate and the like. Examples of the sulfosuccinic acid diester salt include sulfosuccinic acid di-2-ethylhexyl ester sodium salt. Examples of the sulfonate of the aromatic ring-containing compound include mono- or disulfonate of alkylated diphenyl ether and styrenated phenol sulfonate.

  Examples of phosphoric acid ester salts include higher alcohol phosphoric acid ester salts and higher alcohol EO adduct phosphoric acid ester salts. Examples of the higher alcohol phosphate salt include lauryl alcohol phosphate monoester disodium salt and lauryl alcohol phosphate diester sodium salt. Examples of the higher alcohol EO adduct phosphate ester salt include oleyl alcohol EO 5 mol adduct phosphate monoester disodium salt.

--- Cationic surfactant (s-2) ---
As the cationic surfactant (s-2), a quaternary ammonium salt type surfactant, an amine salt type surfactant and the like can be used.

  As the quaternary ammonium salt type surfactant, a tertiary amine having 3 to 40 carbon atoms and a quaternizing agent (for example, alkylating agents such as methyl chloride methyl bromide, ethyl chloride, benzyl chloride and dimethyl sulfate, EO, etc.) For example, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride (benzalkonium chloride), cetylpyridinium chloride, polyoxy Examples thereof include ethylene trimethyl ammonium chloride and stearamide ethyl diethyl methyl ammonium methosulfate.

  As the amine salt type surfactant, a primary to tertiary amine is converted into an inorganic acid (for example, hydrochloric acid, nitric acid, sulfuric acid, hydroiodic acid, phosphoric acid and perchloric acid) or an organic acid (acetic acid, formic acid, glue acid, Lactic acid, gluconic acid, adipic acid, alkylphosphoric acid having 2 to 24 carbon atoms, malic acid, citric acid and the like). Examples of the primary amine salt-type surfactant include inorganic acid salts of aliphatic higher amines having 8 to 40 carbon atoms (for example, higher amines such as laurylamine, stearylamine, cetylamine, hardened tallow amine, and rosinamine). Alternatively, organic acid salts and higher fatty acid (carbon number 8 to 40, stearic acid, oleic acid, etc.) salts of lower amines (2 to 6 carbon atoms) and the like can be mentioned. Examples of the secondary amine salt type surfactant include inorganic acid salts or organic acid salts such as EO adducts of aliphatic amines having 4 to 40 carbon atoms. Examples of the tertiary amine salt type surfactant include aliphatic amines having 4 to 40 carbon atoms (for example, triethylamine, ethyldimethylamine, N, N, N ′, N′-tetramethylethylenediamine, etc.), EO (2 mol or more) adduct of aliphatic amine (2 to 40 carbon atoms), alicyclic amine having 6 to 40 carbon atoms (for example, N-methylpyrrolidine, N-methylpiperidine, N-methylhexamethyleneimine, N-methylmorpholine and 1,8-diazabicyclo (5,4,0) -7-undecene), nitrogen-containing heteroaromatic amines having 5 to 30 carbon atoms (for example, 4-dimethylaminopyridine, N-methyl) Inorganic salts or organic salts of imidazole and 4,4′-dipyridyl, etc.) and triethanolamine monostearate, stearamide ethyl diethylmethyl Such as tertiary inorganic or organic acid salts of amines such as ethanolamine.

--- Amphoteric surfactant (s-3) ---
Examples of the amphoteric surfactant (s-3) include a carboxylate type amphoteric surfactant, a sulfate ester type amphoteric surfactant, a sulfonate type amphoteric surfactant, and a phosphate ester type amphoteric surfactant. Can be used.

  Examples of the carboxylate-type amphoteric surfactants include amino acid-type amphoteric surfactants, betaine-type amphoteric surfactants, and imidazoline-type amphoteric surfactants. The amino acid type amphoteric surfactant is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, and examples thereof include a compound represented by the following general formula (2).

_{[R-NH- (CH 2)} n -COO] m M ··· formula (2)

[Wherein R is a monovalent hydrocarbon group; n is 1 or 2; m is 1 or 2; M is a hydrogen ion, an alkali metal ion, an alkaline earth metal ion, an ammonium cation, an amine cation, And alkanolamine cations. ]

  Examples of the double-sided active agent represented by the general formula (2) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (eg, sodium stearylaminopropionate, sodium laurylaminopropionate); alkyl ( Examples thereof include C4-C24) aminoacetic acid type amphoteric surfactants (such as sodium laurylaminoacetate).

  The betaine-type amphoteric surfactant is an amphoteric surfactant having a quaternary ammonium salt-type cation moiety and a carboxylic acid-type anion moiety in the molecule, for example, alkyl (having 6 to 40 carbon atoms) dimethyl betaine. (Stearyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, etc.), C6-C40 amide betaines (coconut oil fatty acid amidopropyl betaine, etc.), alkyls (C6-C40) dihydroxyalkyls (C6-C40) Examples include betaine (such as lauryl dihydroxyethyl betaine).

  The imidazoline type amphoteric surfactant is an amphoteric surfactant having a cation part having an imidazoline ring and a carboxylic acid type anion part. For example, 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazoli Examples include nitrobetaine.

  Other amphoteric surfactants include, for example, glycine-type amphoteric surfactants such as sodium lauroyl glycine, sodium lauryl diaminoethyl glycine, lauryl diaminoethyl glycine hydrochloride, dioctyl diaminoethyl glycine hydrochloride; sulfobetaines such as pentadecyl sulfotaurine Examples include amphoteric surfactants, sulfonate amphoteric surfactants, and phosphate ester type amphoteric surfactants.

--- Nonionic surfactant (s-4) ---
As the nonionic surfactant (s-4), an AO addition type nonionic surfactant and a polyhydric alcohol type nonionic surfactant can be used.

  AO addition type nonionic surfactants directly add AO (2 to 20 carbon atoms) to higher alcohols having 8 to 40 carbon atoms, higher fatty acids having 8 to 40 carbon atoms or alkylamines having 8 to 40 carbon atoms. Or, a higher fatty acid or the like is reacted with a polyalkylene glycol obtained by adding AO to glycol, or AO is added to an esterified product obtained by reacting a higher fatty acid with a polyhydric alcohol, or a higher fatty acid amide is added. It is obtained by adding AO.

  Examples of AO include EO, PO, and BO. Preferred among these are EO and random or block adducts of EO and PO. The number of moles of AO added is preferably 10 to 50 moles, and among these AOs, 50 to 100% is preferably EO.

  As the AO addition type nonionic surfactant, for example, oxyalkylene alkyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon number 8 to 40) (for example, octyl alcohol EO 20 mol adduct, lauryl alcohol EO 20 mol adduct) , Stearyl alcohol EO 10 mol adduct, oleyl alcohol EO 5 mol adduct, lauryl alcohol EO 10 mol PO 20 mol block adduct, etc.); polyoxyalkylene higher fatty acid ester (alkylene having 2 to 24 carbon atoms, higher fatty acid having 8 to 40 carbon atoms) ) (For example, stearyl acid EO 10 mol adduct, lauryl acid EO 10 mol adduct, etc.); polyoxyalkylene polyhydric alcohol higher fatty acid ester (alkylene having 2 to 24 carbon atoms, polyhydric alcohol having 3 to 40 carbon atoms, higher fatty acid) Carbon number -40) (for example, lauric acid diester of polyethylene glycol (polymerization degree 20), oleic acid diester of polyethylene glycol (polymerization degree 20), etc.); polyoxyalkylene alkylphenyl ether (alkylene having 2 to 24 carbon atoms, alkyl carbon) 8 to 40) (for example, nonylphenol EO 4 mol adduct, norphenol EO 8 mol PO 20 mol block adduct, octylphenol EO 10 mol adduct, bisphenol A / EO 10 mol adduct, styrenated phenol EO 20 mol adduct, etc.); polyoxy Alkylenealkylamino ethers (alkylene having 2 to 24 carbon atoms, alkyl having 8 to 40 carbon atoms) and (for example, laurylamine EO 10 mol adduct, stearylamine EO 10 mol adduct, etc.); polyoxya Xylene alkanolamide (2-24 carbon atoms of alkylene, 8-24 carbon atoms of amide (acyl moiety)) (for example, EO 10 mol adduct of hydroxyethyl lauric acid amide, EO 20 mol adduct of hydroxypropyl oleic acid amide, etc.) Can be mentioned

  As the polyhydric alcohol type nonionic surfactant, polyhydric alcohol fatty acid ester, polyhydric alcohol fatty acid ester AO adduct, polyhydric alcohol alkyl ether, polyhydric alcohol alkyl ether AO adduct and the like can be used. The polyhydric alcohol has 3 to 24 carbon atoms, the fatty acid has 8 to 40 carbon atoms, and the AO has 2 to 24 carbon atoms.

  Examples of the polyhydric alcohol fatty acid ester include pentaerythritol monolaurate, pentaerythritol monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan dilaurate, sorbitan dioleate, and sucrose monostearate.

  Examples of polyhydric alcohol fatty acid ester AO adducts include ethylene glycol monooleate EO 10 mol adduct, ethylene glycol monostearate EO 20 mol adduct, trimethylolpropane monostearate EO 20 mol PO 10 mol random adduct, sorbitan monolaurate. EO 10 mol adduct, sorbitan distearate EO 20 mol adduct, sorbitan dilaurate EO 12 mol PO 24 mol random adduct and the like.

  Examples of the polyhydric alcohol alkyl ether include pentaerythritol monobutyl ether, pentaerythritol monolauryl ether, sorbitan monomethyl ether, sorbitan monostearyl ether, methyl glycoside and lauryl glycoside.

  Examples of the polyhydric alcohol alkyl ether AO adduct include sorbitan monostearyl ether EO 10 mol adduct, methyl glycoside EO 20 mol PO 10 mol random adduct, lauryl glycoside EO 10 mol adduct and stearyl glycoside EO 20 mol PO 20 mol random adduct. Can be mentioned.

-Water-soluble polymer (t)-
Examples of the water-soluble polymer (t) include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin , Chitosan, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, in the sodium hydroxide part of polyacrylic acid) Sodium hydroxide, acrylic acid ester copolymer), styrene-maleic anhydride copolymer sodium hydroxide (Partial) neutralization product, water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.

  The shape of the resin particles (C) obtained by the production method (I) is controlled by controlling the difference in sp value between the resin (a) and the resin (b) and the molecular weight of the resin (a). And particle surface properties can be controlled. When the difference in sp value is small, it is easy to obtain irregularly shaped particles with a smooth surface, and when the difference in sp value is large, it is easy to obtain spherical particles with a rough surface. Moreover, when the molecular weight of the resin (a) is large, particles having a rough surface are easily obtained, and when the resin (a) has a small molecular weight, particles having a smooth surface are easily obtained. However, granulation becomes difficult if the sp value difference between the resin (a) and the resin (b) is too small or too large. If the molecular weight of the resin (a) is too small, granulation becomes difficult. From this, the sp value difference between the preferable resin (a) and the resin (b) is 0.01 to 5.0, more preferably 0.1 to 3.0, and particularly preferably 0.2. ~ 2.0.

  In the case of the production method (II), the shape of the resin particles (C) greatly affects the shape of the resin particles (B) prepared in advance, and the resin particles (C) are almost the same as the resin particles (B). Become a shape. However, when the resin particles (B) are distorted, if a larger amount of the coating agent (W ′) is used in the production method (II), it becomes spherical.

  In the present invention, from the viewpoints of particle size uniformity, storage stability and the like of the resin particles (C), the resin particles (C) are 0.01% to 60% by mass of the resin (a) and 40% by mass to The resin particles (B) containing 99.99% by mass of the resin (b) are preferable, and more preferably 0.1% by mass to 50% by mass of the resin (a) and 50% by mass to 99%. 0.9 mass% resin particles (B), particularly preferably 1 mass% to 45 mass% resin (a) and 55 mass% to 99 mass% resin particles (B). It will be. When the resin (a) is 0.01% by mass or more, the blocking resistance is good, and when it is 60% by mass or less, the fixing characteristics, particularly the low-temperature fixability is good. Further, if the resin particles (B) contain 40% by mass or more of the resin (b), the fixing properties, particularly the low-temperature fixing property are good, and if it is 99.99% by mass or less, the blocking resistance is good. Become.

  Further, from the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C), in the resin particles (C), 5% or more of the surface of the resin particles (B), preferably 30%. As described above, more preferably 50% or more, particularly preferably 80% or more, is covered with the resin (a) (for example, the resin particles (A) or the coating (P)). The surface coverage of the resin particles (C) can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).

  Surface coverage (%) = [area of the portion covered with the resin (a) / area of the portion covered with the resin (a) + area of the portion where the resin particles (B) are exposed] × 100

  From the viewpoint of particle size uniformity, the variation coefficient of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1% to 15%. Moreover, from the particle size uniformity, the value of [volume average particle size (Dv) / number average particle size (Dn)] of the resin particles (C) is preferably 1.0 to 1.4, more preferably. Is 1.0 to 1.3. The volume average particle diameter (Dv) of the resin particles (C) varies depending on the application, but is generally preferably 0.1 μm to 16 μm. The upper limit is more preferably 11 μm, particularly preferably 9 μm, and the lower limit is more preferably 0.5 μm, particularly preferably 1 μm. The volume average particle diameter (Dv) and the number average particle diameter (Dn) can be measured simultaneously with Multisizer III (manufactured by Coulter).

In the present invention, the resin particles (C) have the particle diameters of the resin particles (A) and the resin particles (B) and the coverage of the surface of the resin particles (B) with the coating (P) containing the resin (a). By changing, desired unevenness can be imparted to the particle surface. It is preferable that the BET value specific surface area of the resin particles (C) is 0.5 to 5.0 m ² / g in that the powder fluidity can be improved. In the present invention, the BET specific surface area is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measurement gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). It is. Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of the resin particles (C) is preferably 0.01 μm to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoints of powder flowability, melt leveling properties and the like. In that case, the resin particles (B) are also preferably spherical. The average circularity of the resin particles (C) is preferably 0.95 to 1.00, more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). 100 mL to 150 mL of water from which impure solids have been removed in advance are placed in a predetermined container, and 0.1 mL to 0.5 mL of a surfactant (dry well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1g-9.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) for about 1 to 3 minutes, and the dispersion concentration is 3,000 / μL to 10,000. / ΜL to measure the shape and distribution of the resin particles.

<Other ingredients>
As described above, the toner according to the present invention is a toner including resin particles (C) having the first resin (a) and the resin particles (B) containing the second resin (b), Further, it contains 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. There is no restriction | limiting in particular as a charge control agent, The following each material is mentioned.

  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 0.02 parts by mass to 1 part with respect to 100 parts by mass of the binder resin (resin content in the resin particles (B)). Part by mass is more preferable. 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 between layers of the layered inorganic mineral that can be used as a deforming agent in the present invention is not particularly limited and can be appropriately selected depending on the purpose. A material having a smectite-based basic crystal structure modified with an organic cation is desirable. 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 (3) is more preferable. The following general formula (3) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

_{R 1 (OR 2) n OSO} 3 M ··· formula (3)

[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, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, 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 white, litbon, 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. The reason is that these waxes are finely dispersed in the toner binder resin of the present invention, so that it is easy to obtain a toner excellent in offset prevention, transferability and durability as described later. 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)
The developer according to the present invention contains at least the toner according to the present invention described above, and further contains other components appropriately selected such as a carrier. The developer according to the present invention may be a one-component developer or a two-component developer, but when used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, A two-component developer is preferable from the viewpoint of improving the service life.

<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 a core material, It can select suitably from well-known things. For example, 50-90 emu / g manganese-strontium (Mn-Sr) -based material, manganese-magnesium (Mn-Mg) -based material and the like are preferable, and in terms of securing image density, iron powder (100 emu / g or more), A highly magnetized material such as magnetite (75 to 120 emu / g) is preferred. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu) is advantageous in that it can weaken the contact with the electrostatic latent image carrier (photosensitive member) in which the toner is in a spiked state, and is advantageous in improving the image quality. / G) and the like are preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle size (weight average particle size (D50)) is less than 10 μm, the distribution of carrier particles increases in the number of fine powders, and the magnetization per particle may be lowered, causing carrier scattering. In the case of exceeding the specific surface area, the specific surface area may be reduced, and the toner may be scattered. In the case of a full color having many solid portions, the reproduction of the solid portions may be deteriorated.

  There is no restriction | limiting in particular as a material of the resin layer which coat | covers a core material, According to the objective, it can select suitably from well-known resin. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene Fluoropolymers such as resins, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers A terpolymer (fluorinated triple (multiple) copolymer), a silicone resin, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable in that the effect of preventing toner filming on the carrier is high.

  There is no restriction | limiting in particular as silicone resin which comprises a resin layer, According to the objective, it can select suitably from the silicone resin generally known. For example, a straight silicone resin composed only of an organosilosan bond; a silicone resin modified with an alkyd resin, a polyester resin, an epoxy resin, an acrylic resin, a urethane resin, or the like can be given.

  Commercially available products can be used as the silicone resin. Examples of the straight silicone resin include KR271, KR255, KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Is mentioned.

  Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; Toray Dow SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Corning Silicone Co., Ltd., and the like.

  In addition, although a silicone resin can be used alone, 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 covering the core material may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. It is done. 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 the electric resistance.

  The resin layer covering the core material is prepared by, for example, dissolving a 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 material by a known coating method, followed by drying. It can be formed by baking. 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 an 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 of the resin layer 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% by mass to 5.0% by mass. If it is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. If it exceeds 5.0% by mass, the resin layer becomes too thick and granulates between carriers. May occur, and uniform carrier particles may not be obtained.

  When the developer according to the present invention is a two-component developer, the carrier content 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 image forming method according to the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step and a cleaning step. , Including recycling process, control process, etc.

  The image forming apparatus 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, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means 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 the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

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

<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 according to the present invention, and can be suitably performed by a control unit. 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 according to the present invention by the image forming apparatus according to the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 as an electrostatic latent image carrier (hereinafter referred to as “photosensitive body 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. 1 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. 1, 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 according to the present invention by the image forming apparatus according to the present invention will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 2 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. FIG. 3 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. 2. 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 type 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 each color image corresponding image (L in FIG. 3), and forming an electrostatic latent image corresponding to each color image on the photosensitive member, and this 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 process cartridge used in 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 develop a visible image. At least developing means for forming the image forming apparatus, detachably attached to the main body of the image forming apparatus, and further 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 provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in the image forming apparatus used in the present invention.

  For example, as shown in FIG. 4, 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. 4, 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. 4 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 Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not restrict | limited to the following Example. Of Examples 1 to 15 shown below, Examples 1, 5, 6, 10, 11, and 15 are test examples as reference examples that do not belong to the scope of the present invention.

[Production Example 1] -Production of second resin (b)-
In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube, the raw materials shown in the polyester diol (b11-1) in Table 1 below were heated and melted at 120 ° C. for 20 minutes, and then tin octylate 2 A mass part was added, and ring-opening polymerization was carried out at 160 ° C. for 3 hours at normal pressure, and further reacted at normal pressure and 130 ° C. for 1 hour. The resin taken out was cooled to room temperature, and then pulverized into a polyester diol (b11-1) having a polyhydroxycarboxylic acid skeleton. The number average molecular weight Mn of (b11-1) was 3,000, and the weight average molecular weight Mw was 5,000. The polyester diol (b12) obtained by dehydrating and condensing the raw materials shown in the polyester diol (b12) of Table 1 and the previously obtained polyester diol (b11-1) are dissolved in methyl ethyl ketone, followed by an extender. As an isophorone diisocyanate (IPDI), an extension reaction was carried out at 50 ° C. for 6 hours, and the residual lactide and the solvent were distilled off under reduced pressure to obtain [Resin (b-1)] of Production Example 1. The number average molecular weight Mn of (b-1) was 2,900, and the weight average molecular weight Mw was 13,000. In addition, in the following Table 1, a numerical value shows a mass part.

[Production Example 2]
In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube, the raw materials shown in the polyester diol (b11-2) in Table 2 below were heated and melted at 120 ° C. for 20 minutes, and then tin octylate 2 A mass part was added, and ring-opening polymerization was carried out at 160 ° C. for 10 hours at normal pressure, and further reacted at normal pressure and 130 ° C. for 1 hour. Thereafter, residual lactide was distilled off under reduced pressure to obtain [Resin (b-2)] of Production Example 2. The number average molecular weight of the resin (b-2) was 8,900, and the weight average molecular weight was 35,000. In Table 2 below, the numerical values indicate parts by mass.

[Production Example 3]
The raw materials shown in Table 3 below were added to a four-necked flask and heated and melted at 120 ° C. for 20 minutes in a nitrogen atmosphere. Then, 1 part by mass of tin octylate was added and reacted at 190 ° C. for 3 hours. Thereafter, residual lactide and caprolactone were distilled off under reduced pressure to obtain [Resin (b-3)] of Production Example 3. The number average molecular weight of the resin (b-3) was 9,000, and the weight average molecular weight was 40,000. In addition, in the following Table 3, a numerical value shows a mass part.

[Production Example 4]
In an autoclave reaction vessel equipped with a thermometer, a cooling tube, a stirrer and a nitrogen introduction tube, the raw materials shown in Table 4 below and 2 parts by weight of dibutyltin oxide were placed and reacted at 230 ° C. for 8 hours at normal pressure. After reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by mass of trimellitic anhydride was put in the reaction vessel, and reacted at 180 ° C. and normal pressure for 2 hours. [Resin (b-4)] of Production Example 4 Got. The number average molecular weight of the resin (b-4) was 2,500, and the weight average molecular weight was 6,700. In Table 4 below, the numerical values indicate parts by mass.

[Production Example 5] Synthesis of polyester prepolymer
In a reaction vessel equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen introduction tube, the following components were placed, reacted at 230 ° C. under normal pressure for 8 hours, and then reacted for 7 hours under reduced pressure of 10 to 15 mmHg. An intermediate polyester resin was synthesized.

720 parts by mass of bisphenol A ethylene oxide 2-mole adduct 90 parts by mass terephthalic acid 290 parts by mass trimellitic anhydride 25 parts by mass dibutyltin oxide 2 parts by mass

  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 point (Tg) of 57 ° C., an acid value. Of 0.4 mgKOH / g and hydroxyl value of 49 mgKOH / g.

  Next, the following components were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 8 hours to synthesize [Polyester Prepolymer].

Intermediate polyester resin 400 parts by mass Isophorone diisocyanate 95 parts by mass Ethyl acetate 580 parts by mass

  The obtained polyester prepolymer had a free isocyanate content of 1.42% by mass.

[Production Example 6] Synthesis of ketimine compound
In a reaction vessel in which a stir bar and a thermometer were set, 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 Example 7] -Production of master batch-
The following components were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). However, as the resin, [resins (b-1) to (b-4)] synthesized in Production Examples 1 to 4 were used, respectively.

Water 1,000 parts by mass Carbon black (Printtex 35, manufactured by Degussa) 530 parts by mass (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
1,200 parts by mass of resin

  The obtained mixture was kneaded at 150 ° C. for 30 minutes using a two roll roll, cooled by rolling, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

[Production Examples 8 to 12] -Production of fine particle dispersions (w-1) to (w-5)-
In a 2 liter four-necked flask equipped with a thermometer, a condenser, a stirrer and a nitrogen inlet tube, the following components were put, and the temperature was raised to 90 ° C. while stirring under a nitrogen atmosphere. A urethanization reaction was performed.

Polycaprolactone 70 parts by mass Copolyester resin (*) 80 parts by mass Isophorone diisocyanate 88.8 parts by mass Dimethylolpropionic acid 24 parts by mass Ethyl acetate 60 parts by mass (*) Ethylene glycol (E), Neopentyl glycol (N), Copolyester resin comprising terephthalic acid (T) and isophthalic acid (I) (copolymerization composition: E / N · T / I = 50/50 · 50/50 (molar ratio))

  Subsequently, 90 parts by mass of ethyl acetate was added dropwise over 30 minutes, and the reaction was further continued at 90 ° C. for 1 hour. Thereafter, the mixture was cooled to 40 ° C. to obtain an NCO-terminated prepolymer. Next, 16 parts by mass of triethylamine was added to the prepolymer for neutralization, and then 500 parts by mass of ion-exchanged water was added. Next, 12.6 parts by mass of adipic acid dihydrazide and 22.7 parts by mass of a dihydrazide compound (Ajinomoto Co., Inc.) were added to the reaction system, and after stirring at 50 ° C. for 1 hour, ethyl acetate was distilled off under reduced pressure. A hydrazide terminated polyurethane aqueous dispersion was obtained. The solid content of this aqueous resin was 37.1%.

  Table 5 below shows 150 parts by mass of ion-exchanged water and the polyurethane aqueous dispersion synthesized in the above section in a 2-liter four-necked flask equipped with a thermometer, a condenser, a stirrer, a nitrogen inlet tube and a dropping funnel. It was added in parts by mass, and the temperature was raised to 80 ° C. over 30 minutes from room temperature. From the dropping funnel, a mixture of acrylic polymer raw materials shown in Table 5 below was dropped over 4 hours, and stirring was continued for 1 hour after completion of the dropping. Next, 1 part by mass of hydrogen peroxide was added and stirring was continued at 80 ° C. for 2 hours to complete the graft polymerization reaction, whereby [fine particle dispersions (w-1) to (w-5)] were obtained.

  The composition ratio and volume average particle size of polyurethane and acrylic polymer of the obtained resin fine particles were as shown in Table 5. In Table 5, the numerical values indicate parts by mass.

[Production Example 13] -Production of fine particle dispersion (w-6)-
The following components were charged in a reaction vessel equipped with a stirrer and a thermometer, and stirred at 400 rpm for 15 minutes to obtain a white emulsion.

Water 683 parts by weight Sodium salt of methacrylic acid ethylene oxide adduct sulfate 11 parts by weight (Eleminol RS-30, manufactured by Sanyo Chemical Industries)
Styrene 68 parts by weight Methacrylic acid 102 parts by weight Butyl acrylate 103 parts by weight Butyl thioglycolate 6 parts by weight Ammonium persulfate 1 part by weight

  This emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts by weight of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain [fine particle dispersion (w-6)]. The volume average particle diameter of the resin fine particles was 105 nm.

[Production Examples 14 to 19] -Preparation of aqueous medium-
300 parts by mass of ion-exchanged water and 300 parts by mass of [fine particle dispersions (w-1) to (w-6)] produced in Production Examples 8 to 13 and 0.2 part by mass of sodium dodecylbenzenesulfonate were mixed. The mixture was stirred and dissolved uniformly to prepare [Aqueous medium phase (1) to (6)]. [Aqueous medium phases (1) to (6)] correspond to those obtained from [fine particle dispersions (w-1) to (w-6)], respectively.

[Production Examples 20 to 23] -Preparation of resin solution-
[Resin (b-1)-(b-4)], [Polyester prepolymer], and 80 parts by mass of ethyl acetate obtained in Production Examples 1 to 4 in the number of parts shown in Table 6 were added and stirred. Thus, [resin solutions (1) to (4)] were prepared. [Resin solutions (1) to (4)] respectively correspond to those obtained from [Resin (b-1) to (b-4)]. In Table 6 below, the numerical values indicate parts by mass.

[Production Examples 24-27] -Preparation of oil phase-
Next, each 400 parts by mass of the resin solutions (1) to (4) obtained in Production Examples 20 to 23 was added to carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration rate 1.7 mm). (40 ° C.)) 5 parts by mass and 5 parts by mass of master batch, and using a bead mill Ultra Visco Mill (manufactured by Imex), liquid feeding speed 1 kg / hour, disk peripheral speed 6 m / second, particle size Three passes were performed under the condition of filling 80% by volume of 0.5 mm zirconia beads. Furthermore, 2.5 parts by mass of a ketimine compound was added and dissolved to obtain [oil phases (1) to (4)]. [Oil phases (1) to (4)] correspond to those obtained from [Resin solutions (1) to (4)], respectively.

[Production Example 28] -Preparation of toner base-
Next, 150 parts by mass of each of [Aqueous medium phases (1) to (6)] obtained in Production Examples 14 to 19 is placed in another container, and a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used. Using, while stirring at 12,000 rpm, 100 parts by mass of [oil phase (1) to (4)] obtained in Production Examples 24-27 as shown in Table 7 below were added and mixed for 10 minutes. An emulsified slurry was obtained. Furthermore, 100 parts by mass of the emulsified slurry was charged in 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 dispersed slurry.

  Next, 100 parts by mass of the dispersed slurry 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 at 12,000 rpm for 10 minutes 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. 20 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the obtained filter cake, and it mixed under 12,000 rpm for 30 minutes using TK type homomixer, Then, it filtered under reduced pressure. 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 base particles.

  Toner bases 1 to 19 produced as in Production Example 28 are shown in Table 7. In addition, in the following Table 7, a numerical value shows a mass part.

[Production Example 29] -Production of toner-
100 parts by mass of the obtained toner base particles 1 to 19 and 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Then, the mixture was mixed for 30 seconds at a peripheral speed of 30 m / second and rested for 1 minute for 5 cycles, and then sieved with a mesh having an opening of 35 μm to prepare toners 1 to 19.

[Production Example 30] -Production of carrier-
The following components were added to 100 parts by mass of toluene and dispersed with a homomixer for 20 minutes to prepare a resin layer coating solution.

Silicone resin (organostraight silicone) 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass

  Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts by mass of spherical magnetite having a volume average particle size of 50 μm to prepare a carrier.

[Production Example 31] -Production of developer-
Each developer of Examples 1 to 15 and Comparative Examples 1 to 4 was prepared by mixing 5 parts by mass of each of the toners 1 to 19 and 95 parts by mass of the carrier.

  Next, the average particle size, fixability, heat-resistant storage stability, charging stability, and environmental fluctuation were evaluated using the obtained developers according to the following evaluation methods. The results are shown in Table 8 below.

<Evaluation method>
<< Measurement of Volume Average Particle Size (Dv), Number Average Particle Size and Ratio (Dv / Dn) >>
The particle size distribution of the toner (toner base particles) was performed using a Coulter Multisizer. That is, Coulter Multisizer III (manufactured by Coulter Co.) is used as a measuring device, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting number distribution and volume distribution is connected to a personal computer. Was used to prepare a 1 mass% NaCl aqueous solution. As a measurement method, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 to 150 mL of the aqueous solution as the electrolytic solution, and 2 to 20 mg of a measurement sample is further added. Dispersion treatment was performed for about 1 to 3 minutes. Further, 100 to 200 mL of an electrolytic aqueous solution was put into another beaker, and the sample dispersion was added to a predetermined concentration therein, and 50,000 particles were used with the Coulter Multisizer III as a 100 μm aperture. The average of was measured. From the obtained volume average particle diameter (Dv) and number average particle diameter (Dn), the ratio (Dv / Dn) between them was determined.

<< Fixability >>
As a fixing roller, an electrophotographic copying machine using a Teflon (registered trademark) roller (MF-200, manufactured by Ricoh Co., Ltd.) is used to change the temperature of the fixing belt, by changing the fixing unit. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on a paper and cardboard transfer paper type 6200 (manufactured by Ricoh Co., Ltd.) and copy printing paper <135> (manufactured by NBS Ricoh Co., Ltd.). . At this time, the upper limit temperature at which hot offset does not occur on plain paper was taken as the fixing upper limit temperature. Further, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with a pad was 70% or more was defined as the minimum fixing temperature. The fixing upper limit temperature and the fixing lower limit temperature thus obtained were evaluated based on the following evaluation criteria.

[Evaluation criteria for maximum fixing temperature]
A: Fixing upper limit temperature is 190 ° C. or higher B: Fixing upper limit temperature is 180 ° C. or higher and lower than 190 ° C. C: Fixing upper limit temperature is 170 ° C. or higher and lower than 180 ° C. D: Fixing upper limit temperature is lower than 170 ° C.
A: Fixing lower limit temperature is less than 135 ° C. B: Fixing lower limit temperature is from 135 ° C. to less than 145 ° C. C: Fixing lower limit temperature is from 145 ° C. to less than 155 ° C. D: Fixing lower limit temperature is 155 ° C. or more

<< Heat-resistant storage stability (Penetration) >>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.

〔Evaluation criteria〕
A: Needle penetration 25 mm or more B: Needle penetration 15 mm or more and less than 25 mm C: Needle penetration 5 mm or more and less than 15 mm D: Needle penetration less than 5 mm

<< Charging stability >>
The developer was set in a commercially available digital full-color printer (image Neo Neo C455 manufactured by Ricoh Co., Ltd.), and a running evaluation of 300,000 sheets was performed with an image chart of 50% image area in a single color mode. The judgment was made based on the amount of charge reduction of the carrier after the running. The amount of change in charge as used herein means that the humidity is adjusted in an unsealing system for 30 minutes or more in an environment where the temperature is 23 ° C. and the relative humidity is 50% (M / M environment). After adding 452 g to a stainless steel container, the sample was sealed and YS-LD (shaking machine manufactured by Yayoi Co., Ltd.) operated for 5 minutes at a scale of 150 for friction charging with an amplitude of about 1100 times. From the charge amount (Q1) measured by a general blow-off method [manufactured by Toshiba Chemical Co., Ltd .: TB-200], the carrier in which the toner in the developer after running can be removed by the blow-off device, This is an amount obtained by subtracting the charge amount (Q2) measured by the same method as that of the method (ΔQ = | Q1-Q2 |).

〔Evaluation criteria〕
A: Charge amount change amount is less than 10 μc / g B: Charge amount change amount is 10 μc / g or more and less than 15 μc / g C: Charge amount change amount is 15 μc / g or more and less than 20 μc / g D: Charge amount change amount is 20 μc / g g or more

<< Environmental change >>
The developer obtained was stirred with a ball mill for 5 minutes in an environment with an air temperature of 23 ° C. and a relative humidity of 50% (M / M environment), and 1.0 g of the developer was sampled to obtain a blow-off charge measuring device (Kyocera Chemical TB-200) was used, and the measured value after nitrogen blowing for 1 minute was used as the charge amount. Further, each developer is measured under two conditions: an environment with an air temperature of 40 ° C. and a relative humidity of 90% (H / H environment), and an environment with an air temperature of 10 ° C. and a relative humidity of 30% (L / L environment). The charge amount of was evaluated. The environmental variation rate was calculated from the following formula based on the charge amount thus obtained, and the calculated environmental variation rate was evaluated based on the following evaluation criteria. It can be said that the lower the environmental fluctuation rate, the more stable the charging property.

  In the above formula (4), [L / L] represents the charge amount in the L / L environment, and [H / H] represents the charge amount in the H / H environment.

〔Evaluation criteria〕
A: Environmental change rate is less than 40% B: Environmental change rate is 40% or more and less than 50% C: Environmental change rate is 50% or more and less than 60% D: Environmental change rate is 60% or more

<Comprehensive evaluation>
From the above evaluation results, a comprehensive judgment was made and the evaluation was made according to the following criteria. In addition, as for comprehensive evaluation criteria, A and B pass, and C and D do not pass.

〔Evaluation criteria〕
A: Very good B: Good C: Bad D: Extremely bad

  A toner in which particles of resin (a) composed of a polyurethane-acrylic polymer composite are attached to the surface of a resin containing a polyhydroxycarboxylic acid skeleton achieves both low-temperature fixability and heat-resistant storage stability as well as charging stability. Good results were also obtained for environmental fluctuations. On the other hand, the toner having particles composed of styrene-acrylic resin on the surface showed deterioration in heat-resistant storage stability, charging stability, and environmental fluctuation. Further, although the resin (a) particles composed of the polyurethane-acrylic polymer composite exist on the surface, the toner having no polyhydroxycarboxylic acid skeleton in the binder resin has greatly deteriorated the low-temperature fixability.

  The toner for image formation according to the present invention is suitable for high-quality electrophotographic image formation because it achieves both fixability and storage stability and provides good image quality over a long period of time. The developer using the toner of the present invention can be widely used in full-color copying machines, full-color laser printers, full-color plain paper fax machines and the like using an electrophotographic multicolor image developing system.

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-A-9-319144 JP 2002-284881 A Japanese Patent No. 3640918 Japanese Patent No. 2909873 Japanese Patent Laid-Open No. 9-274335 JP 2001-166537 A JP 7-33861 A JP 59-96123 A JP 2008-262179 A JP-A-60-186851 JP-A-60-186852 JP-A-60-186854 Japanese Patent No. 3789522 Japanese Patent No. 3289598 JP-A-11-305479 JP 2004-354707 A JP 2005-202299 A JP-A-57-179860 JP-A-5-107797 JP 2008-107678 A

Claims (13)

A toner comprising resin particles (C) having a first resin (a) and resin particles (B) containing a second resin (b),
The resin (a) is composed of a polyurethane-acrylic polymer composite, and is attached to the surface of the resin particles (B).
The resin (b) is to have a non-crystalline polyhydroxycarboxylic acid skeleton,
A toner wherein the composition ratio of polyurethane and acrylic polymer contained in the resin (a) is 2: 8 to 6: 4 . The resin (b) has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and has an optical purity X (%) represented by the following formula (1) of 80% or less. The toner described.
Optical purity X (%) = | X (L form) -X (D form) | ... Formula (1)
[However, X (L-form) represents the L-form ratio (mol%) contained in the resin (b) in terms of optically active monomer, and X (D-form) represents the resin (in terms of optically active monomer) ( The D-form ratio (mol%) contained in b) is represented. ]   The toner according to claim 1, wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms.   The toner according to any one of claims 1 to 3, wherein the resin (b) contains a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton.   The resin (b) is a linear polyester system obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than the polyester diol (b11) together with an extender. The toner according to claim 1, further comprising a resin (b1).   The toner according to claim 5, wherein a mass ratio of the polyester diol (b11) to the polyester diol (b12) is 31:69 to 90:10.   The said resin (b) contains the said linear polyester-type resin (b1) and resin (b2) formed by reaction with a precursor (b0), The Claim 5 or 6 characterized by the above-mentioned. Toner. The toner according to claim 5 , wherein the extender is diisocyanate or dicarboxylic acid .   A developer comprising the toner according to claim 1.   The developer according to claim 9, further comprising a carrier. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image using the toner according to claim 1 to form a visible image;
A transfer step of transferring the visible image to a recording medium;
And a fixing step of fixing the transferred image transferred to the recording medium to the recording medium. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image with the toner according to claim 1 to form a visible image;
Transfer means for transferring the visible image to a recording medium;
An image forming apparatus comprising: fixing means for fixing the transferred image transferred to the recording medium to the recording medium. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developing unit that develops the electrostatic latent image using the toner according to claim 1 to form a visible image, and is detachable from the main body of the image forming apparatus. Process cartridge characterized by.

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