JP2012168219A - Toner, developer, image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which can be favorably adhered to the surface of a polyester resin as dispersion stabilizer even if a polylactic acid skeleton is used as a binder resin, secures heat-resistant preservability, has improved low-temperature fixability, has excellent charging stability for changes in use environment, such as image density, temperature or humidity and excellent charging stability in outputting a large amount of images, and to provide a developer using the toner, an image forming method and an image forming device.SOLUTION: The toner comprises: a resin particle (C) having a first resin (a) and a resin particle (B) containing a second resin (b). The resin (a) is adhered on the surface of the resin particle (B). The resin (a) is a polyester resin. The resin (b) has an amorphous polyhydroxycarboxylic acid skeleton. A difference in SP value between the resin (a) and the resin (b) is 0.1-2.3.

Description

  The present invention relates to a new and improved toner, a developer and a production method thereof, an image forming method and an image forming apparatus using the toner and the developer.

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, to obtain a copy image having 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 are removed by wind centrifugal classification instead of a sieve. There is a problem that the 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 obtained toner has an adverse effect on the fluidity, developability, durability, image quality, and the like. There is a problem.

  Therefore, in Japanese Patent Application Laid-Open No. 9-319144 of Patent Document 1 and Japanese Patent Application Laid-Open No. 2002-284881 of Patent Document 2, an organic solvent solution of a resin previously synthesized by a polymerization reaction is dispersed in a surfactant or a water-soluble resin. There has been proposed a dissolved resin suspension method in which a toner is obtained by dispersing in an aqueous medium in the presence of a (auxiliary) agent and a dispersion stabilizer such as inorganic fine particles and resin fine particles, and removing the solvent by heating, decompression, etc. . 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 Japanese Patent No. 3640918 of 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, Japanese Patent No. 2909873 of Patent Document 4 proposes using polylactic acid as a binder resin. However, when polylactic acid is used as it is as in this proposal, since the concentration of ester bonds is higher than that of the polyester resin, there is a problem that the toner becomes very hard, the grindability is poor, and the productivity is inferior. Therefore, it is considered effective to use a dissolving resin suspension method as described in Patent Documents 1 to 3 to produce a toner without pulverizing and classifying polylactic acid having high hardness and poor grindability. Since the L-form or D-form alone has high crystallinity, the solubility in an organic solvent is extremely low, and it is difficult to use the dissolved resin suspension method.
In contrast, in Japanese Patent Application Laid-Open No. 2010-122667 of Patent Document 5, we have already mixed L-form and D-form of polylactic acid to reduce crystallinity and improve solubility in organic solvents. Have proposed a method for producing toner by a dissolved resin suspension method.

  That is, in Japanese Patent Application Laid-Open No. 2010-122667 of Patent Document 5, a high-quality image having excellent image density, fixability, and heat-resistant storage stability, excellent releasability at low temperatures, little filming, and In order to provide a toner that can be stably obtained, a method for producing the toner, and a developer using the toner, the resin contains a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, Polyhydroxycarboxylic acid skeleton composed of monomers has optical purity X (%) = | X (L form) −X (D form) | [where X (L form) is L form in terms of optically active monomer. The ratio (mol%), X (D form) represents the D form ratio (mol%) in terms of optically active monomer], and the toner is 80% or less.

  The technique described in this publication mentions PLA as a specific example of the polyhydroxycarboxylic acid skeleton, and is certainly similar to the present invention in that | X (L form) -X (D form) | is 80% or less. There is a point. However, as a result of subsequent studies, it has been found that the above-described problems of poor image density, poor charging stability with respect to changes in the usage environment such as temperature and humidity, and poor charging stability when outputting a large amount of images cannot be solved.

That is, 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. In order to solve these problems, attempts have been made to use organic fine particles as a dispersion stabilizer at the time of toner production and attach them to the surface of the toner particles to form a shell. However, although these have 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. Since polylactic acid has a large number of polar groups, it has high hydrophilicity and is relatively difficult to granulate by suspending a dissolved resin solvent solution in an aqueous medium. Distribution tends to be non-uniform. As a result, the toner charge amount varies, the image density becomes non-uniform, and transfer dust occurs. Also, the toner fine powder causes filming on the carrier and the charging member. Furthermore, when a large amount of image is output, the resin fine particles on the surface peel off due to long-term stirring in the developing unit, and the shell forms a film on the charging member, or the fluidity is lowered, so that the charging stability of the toner is deteriorated. I found that there was a problem.

  In the present invention, even when a polylactic acid skeleton is used as a binder resin, the polyester resin, which is a dispersion stabilizer, has good adhesion to the surface, and has excellent low-temperature fixability while ensuring heat-resistant storage stability. An object of the present invention is to provide a toner having good charging stability against changes in use environment such as density, temperature and humidity, and charging stability when outputting a large amount of image, and a developer, an image forming method and an image forming apparatus using the toner. And

The above-described problems of the present invention are solved by the toners and developers described in the following (1) to (15), an image forming method and an image forming apparatus using them.
(1) “Toner including resin particles (C) having a first resin (a) and resin particles (B) containing a second resin (b), wherein the resin (a) is The resin particles (B) are attached to the surface, the resin (a) is a polyester resin, and the resin (b) has an amorphous polyhydroxycarboxylic acid skeleton, A toner characterized in that the SP value difference between the resin (a) and the resin (b) is 0.1 to 2.3.
(2) “The toner according to item (1), wherein an SP value difference between the resin (a) and the resin (b) is 0.3 to 0.8”.
(3) “The toner according to item (1) or (2), wherein the resin (a) has a volume average particle diameter Dv (a) of 35 nm to 400 nm.”
(4) “The toner according to any one of (1) to (3) above, wherein the glass transition point Tg (a) of the resin (a) is 55 to 100 ° C.”
(5) Any one of the items (1) to (4), wherein the resin (a) is a resin having a polyester unit composed of at least a polybasic acid and a polyhydric alcohol. The toner described. "
(6) “The resin (b) has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and the optical purity X (%) of the resin (b) represented by the following formula (1) is 80% or less. The toner according to any one of (1) to (5), wherein the toner is present.
Optical purity X (%) = | X (L isomer) −X (D isomer) | 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. ]

(7) “Item (1) to Item (6)”, wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerization of a hydroxycarboxylic acid having 3 to 6 carbon atoms. The toner according to any one of "."
(8) The toner according to any one of (1) to (7), wherein the resin (b) contains a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton. . "
(9) “The resin (b) is a linear chain obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton with a polyester diol (b12) other than the polyester diol (b11) together with an extender. The toner according to any one of (1) to (8) above, which contains a polyester resin (b1) in the form of a powder.
(10) The mass ratio of the polyester diol (b11) having a polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than the polyester diol (b11) is 31:69 to 90:10. The toner according to item (9). "
(11) “The resin (b) contains a linear polyester resin (b1) and a resin (b2) obtained by reacting the precursor (b0) ( The toner according to any one of items 1) to (10). "
(12) “A developer comprising the toner according to any one of items (1) to (11)”.
(13) “The developer according to item (12), further including a carrier.”
(14) “An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image according to any one of (1) to (11)” At least a developing process for forming a visible image by developing the toner, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. An image forming method characterized by that. "
(15) “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 the above-mentioned items (1) to ( A developing unit that forms a visible image by developing with the toner according to any one of 11), a transfer unit that transfers the visible image to a recording medium, and a fixing of the transferred image transferred to the recording medium An image forming apparatus including at least a fixing unit.

  As is clear from the following detailed and specific description, according to the present invention, even when a polylactic acid skeleton is used as the binder resin, the polyester resin as a dispersion stabilizer adheres well to the surface. , A toner having excellent low-temperature fixability while ensuring heat-resistant storage stability, excellent charging stability against changes in the use environment such as image density, temperature and humidity, and charging stability when outputting a large amount of images, and this toner An extremely excellent effect that a developer, an image forming method, and an image forming apparatus can be provided is achieved.

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.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings.

(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 attached to the surface of the resin particles (B), the resin (a) is a polyester resin, and the resin (b) has an amorphous polyhydroxycarboxylic acid skeleton, The SP value difference between the resin (a) and the resin (b) is 0.1 to 2.3. 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 raising processes in which the temperature is raised from 20 ° C. to 250 ° C. at 10 ° C./min, neither shows 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 hydroxycarboxylic acids 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 isomer) −X (D isomer) | 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 isomer) (%) = 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. 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 (such as bisphenol A, bisphenol F, and bisphenol S) (alkylene oxide is abbreviated as AO hereinafter). ), 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.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam 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 terminal.
Method [2] The functional group of the component is left at the terminal by excessively using one of the two or more components, and further contains a functional group and a reactive group capable of reacting with the remaining functional group A method of reacting a compound.

  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 alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.) and alkenyl succinic acid (dodecenyl succinic 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). Furthermore, 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)). And glass transition point (hereinafter abbreviated as Tg).

  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.

  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
Detector: Refractive index detector Reference material: TOSOH standard polystyrene (TSK standard POLYSTYRENE) 12 points (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
Detector: Refractive index detector Reference material: TOSOH standard polystyrene (TSK standard POLYSTYRENE) 12 points (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 Seiko Denshi Kogyo Co., Ltd. DSC20 and SSC / 580.

  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 a polyester resin. If it is configured, the shape, structure, and size are not limited, and may be appropriately selected according to the purpose. However, the resin particles (A) or the coated particles (P) are formed as resin particles (B). It is preferable that it exists in the surface. 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 bonded to the surface portion when an organic solvent, an active hydrogen-containing compound (amines), and a resin (b) are dispersed in an aqueous medium to form organic dispersed fine particles. It is considered that the toner particles obtained thereby are unevenly distributed mainly on the surface portion.

  The resin (a) is a polyester resin and is not particularly limited as long as it is composed of a polybasic acid and a polyhydric alcohol, and can be appropriately selected according to the purpose. The constituent components of these polyester resins (a) will be described below.

  Examples of the aromatic dicarboxylic acid among the polybasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. Sodium sulfoisophthalic acid or 5-hydroxyisophthalic acid can be used. Examples of aliphatic dicarboxylic acids include oxalic acid, (anhydrous) succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, and the like, fumaric acid, (anhydrous) maleic acid, (anhydrous) ) Unsaturated dicarboxylic acids such as itaconic acid, (anhydrous) citraconic acid, dimer acid and the like. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid (anhydride), tetrahydrophthalic acid (anhydride), and the like.

  The total content of aromatic polybasic acids in the total acid component is preferably 50 mol% or more. When this value is less than 50 mol%, the structure derived from the aliphatic polybasic acid and the alicyclic polybasic acid accounts for the majority of the resin skeleton, so the hardness, stain resistance, and water resistance of the formed film The storage stability of the aqueous dispersion may be reduced because aliphatic and / or alicyclic ester bonds have lower hydrolysis resistance than aromatic ester bonds. In order to ensure the storage stability of the aqueous dispersion, the content of the aromatic polybasic acid in the total acid component is preferably 70 mol% or more, and the processing is performed while balancing with other performances of the formed film. In order to improve the properties, water resistance, chemical resistance and weather resistance, 65 mol% or more of the total acid component constituting the polyester resin is terephthalic acid, in order to achieve the object of the present invention. Particularly preferred.

On the other hand, about a polyhydric alcohol component, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, and ether bond containing glycol can be mentioned as glycol. Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, etc. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol. Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, for example 2,2 -Bis (4-hydroxyethoxyphenyl) propane and the like can be mentioned.
Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used as necessary. However, since the ether structure lowers the water resistance and weather resistance of the polyester resin coating, the amount used is preferably 10% by weight or less, more preferably 5% by weight or less of the total polyhydric alcohol component.

  In the present invention, it is preferable that 50 mol% or more, particularly 65 mol% or more of the total polyhydric alcohol component of the polyester resin is composed of ethylene glycol and / or neopentyl glycol. Since ethylene glycol and neopentyl glycol are industrially produced in large quantities, they are inexpensive and well-balanced in the performance of the coating film formed.Ethylene glycol components are particularly resistant to chemicals, and neopentyl glycol components are particularly advantageous. It has the advantage of improving weather resistance.

  The polyester resin used as the resin (a) in the present invention can copolymerize a tribasic or higher polybasic acid and / or a polyhydric alcohol as necessary. (Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2, 3,4-butanetetracarboxylic acid or the like is used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as the polyhydric alcohol having three or more functions. A tribasic or higher polybasic acid and / or polyhydric alcohol is copolymerized in an amount of 10 mol% or less, preferably 5 mol% or less, based on the total acid component or the total alcohol component. The high processability of the coating, which is an advantage of the polyester resin, is not expressed.

  If necessary, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and ester-forming derivatives thereof, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid , High-boiling monocarboxylic acids such as 4-hydroxyphenyl stearic acid, stearyl alcohol, high-boiling monoalcohols such as 2-phenoxyethanol, hydroxycarboxylics such as ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid An acid or an ester-forming derivative thereof may be used.

  Such a polyester resin is synthesized from the above monomers using a known method. For example, (a) an esterification reaction is performed by reacting all monomer components and / or a low polymer thereof in an inert atmosphere at 180 to 250 ° C. for about 2.5 to 10 hours, followed by 1 Torr in the presence of a catalyst. A method of obtaining a polyester resin by proceeding a polycondensation reaction under a reduced pressure at a temperature of 220 to 280 ° C. until a desired melt viscosity is reached, and (b) a stage before the polycondensation reaction reaches a target melt viscosity. The reaction product is mixed with a chain extender selected from polyfunctional epoxy compounds, isocyanate compounds, oxazoline compounds, etc. in the next step, and the reaction product is reacted for a short time to achieve a high molecular weight, (C) The polycondensation reaction is advanced to the target melt viscosity or higher, the monomer component is further added, and the depolymerization is performed in an inert atmosphere, normal pressure to pressurized system. The method or the like to obtain a polyester resin melt viscosity which can be exemplified.

  It is preferable from the viewpoint of the water resistance of the formed film that the carboxyl group necessary for the aqueous formation is unevenly distributed at the terminal of the resin molecular chain rather than being present in the resin skeleton. As a method for introducing a specific amount of carboxyl group into the molecular chain terminal of a high molecular weight polyester resin without causing side reaction or gelation, the polycondensation reaction in the above method (a) is used when producing a polyester resin. A method of adding a tribasic or higher polybasic acid component after the start of the step, or adding a polybasic acid anhydride immediately before the end of the polycondensation reaction, most of the molecules in the method (b) Preferred embodiments include a method of increasing the molecular weight of a low molecular weight polyester resin having a carboxyl group at the chain end using a chain extender, a method of using a polybasic acid component as a depolymerizing agent in the method (c), and the like.

  The content of the polyester resin in the polyester resin aqueous dispersion should be appropriately selected according to the intended use, dry film thickness, and molding method, but is generally 0.5 to 50% by weight, particularly 1 to 40%. It is preferable to use in the range of% by weight. As will be described later, the aqueous polyester resin dispersion of the present invention has an advantage of excellent storage stability even at a high solid content concentration of 20% by weight or more. However, when the content of the polyester resin exceeds 50% by weight, the viscosity of the polyester resin aqueous dispersion is remarkably increased, which may make it difficult to form the material substantially.

[Basic compounds]
The polyester resin of the resin (a) in the present invention is neutralized with a basic compound when dispersed in an aqueous medium. In the present invention, neutralization reaction with the carboxyl group in the polyester resin is the starting force for aqueous formation (formation of resin fine particles), and furthermore, a very small amount of protective colloid action described later by the electric repulsion between the generated carboxy anions. By using in combination with the compound having, aggregation between the fine particles can be prevented. As the basic compound, a compound that volatilizes at the time of film formation or baking and curing by adding a curing agent is preferable, and examples thereof include ammonia and organic amine compounds having a boiling point of 250 ° C. or less. Examples of desirable organic amine compounds include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine , Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, Triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like can be mentioned. The basic compound is preferably added in an amount that can be at least partially neutralized according to the carboxyl group contained in the polyester resin, that is, 0.2 to 1.5 times the equivalent of the carboxyl group. It is more preferable to add 4-1.3 times equivalent. When the amount is less than 0.2 times equivalent, the effect of adding a basic compound is not recognized, and when the amount exceeds 1.5 times equivalent, the polyester resin aqueous dispersion may be significantly thickened.

[Amphiphilic organic solvent]
In the present invention, an amphiphilic organic compound having a plasticizing ability with respect to the polyester resin is required in the aqueous treatment step for the purpose of accelerating the aqueous treatment speed. However, if the boiling point exceeds 250 ° C, the evaporation rate is so slow that it cannot be removed sufficiently even when the coating is dried. So-called general-purpose compounds called organic solvents are targeted.

The characteristics required for the organic solvent referred to in the present invention are that it is amphiphilic and has a plasticizing ability for the polyester resin. Here, the amphiphilic organic solvent means a solvent having a solubility in water at 20 ° C. of at least 5 g / L or more, preferably 10 g / L or more. When the solubility is less than 5 g / L, the effect of accelerating the aqueous treatment speed is poor. Moreover, the plasticizing ability of the organic solvent can be determined by the following simple test. That is, a 3 cm × 3 cm × 0.5 cm (thickness) square plate is made from a target polyester resin, immersed in 50 ml of an organic solvent, and allowed to stand in an atmosphere at 25 to 30 ° C. The shape of the square plate is clearly deformed after 3 hours, or when a 0.2 cm diameter stainless steel round bar is brought into contact while statically applying a force of 1 kg / cm ^{2 in} the thickness direction. In addition, when 0.3 cm or more of the round bar enters the square plate, it is judged that the organic solvent has plasticizing ability. An organic solvent that is judged to have no plasticizing ability has a poor effect of accelerating the aqueous treatment speed.

  Such organic solvents include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl. Alcohols such as -1-propanol, 2-methyl-1-propanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone, ethers such as tetrahydrofuran and dioxane, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, Esters such as ethyl acrylate, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diglycol derivatives such as diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol methyl ether acetate, and further, 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetate Nitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, may be mentioned ethyl acetoacetate. These solvents can be used singly or in combination of two or more.

Among these exemplified organic solvents, when a compound satisfying the following two conditions is used singly or when two or more compounds are mixed and used, the effect of accelerating the aqueous treatment is not only excellent. And the resulting polyester resin aqueous dispersion is excellent in storage stability, which is preferable.
(Condition 1) The molecule has a hydrophobic structure in which 4 or more carbon atoms are directly bonded. (Condition 2) At least one atom having a Pauling electronegativity of 3.0 or more is present at the end of the molecule. The chemical shift of the 13C-NMR (nuclear magnetic resonance) spectrum of a carbon atom having a substituent to be contained and directly bonded to an atom having an electronegativity of 3.0 or more in the substituent is at room temperature in CDCl3. Having a polar substituent such that it is 50 ppm or more as measured by

  Examples of the substituents defined by Condition 2 include alcoholic hydroxyl groups, methyl ether groups, ketone groups, acetyl groups, methyl ester groups and the like. Among compounds satisfying the above two conditions, as a particularly suitable organic solvent, N-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, alcohols such as n-hexanol and cyclohexanol, methyl isobutyl ketone, Ketones such as cyclohexanone, esters such as n-butyl acetate, isobutyl acetate, sec-butyl acetate, and 3-methoxybutyl acetate, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol Glycol derivatives such as monobutyl ether, and further, can be exemplified 3-methoxy-3-methylbutanol, 3-methoxybutanol.

  If such organic solvent has a boiling point of 100 ° C. or lower or can be azeotroped with water, a part or all of the organic solvent may be removed (stripped) during or after the aqueous process. In the end, it should be contained in an amount of 0.5 to 10% by weight, preferably 0.5 to 8.0% by weight, more preferably 1.0 to 5.0% by weight based on the polyester resin aqueous dispersion. It is. A polyester resin aqueous dispersion contained in an amount of 0.5 to 10% by weight is excellent in storage stability and excellent in film formability. If it is less than 0.5% by weight, there are problems that it takes a long time to make it aqueous, and polyester resin fine particles having a desirable particle size distribution may not be produced. On the other hand, if the amount exceeds 10% by weight, not only the original purpose of the aqueous dispersion is impaired, but also the viscosity of the aqueous dispersion becomes abnormally high due to the increased proportion of secondary particles in the aqueous dispersion described later. , The storage stability may be inferior and the film forming property may be inferior.

[Compound having protective colloid action]
In the present invention, a compound having a protective colloid action is used as necessary for the purpose of removing the organic solvent out of the system (stripping) or ensuring the stability of the aqueous dispersion during storage. . The protective colloid referred to in the present invention is adsorbed on the surface of resin fine particles in an aqueous medium, and exhibits a stabilizing effect called “mixing effect”, “osmotic pressure effect” or “volume limiting effect”, and exhibits a stabilizing effect between resin fine particles. The action which prevents adsorption | suction. As a compound having protective colloid action, polymerization of a vinyl monomer containing polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid, acrylic acid and / or methacrylic acid as one component Products, polyitaconic acid, gelatin, gum arabic, casein, swellable mica and the like. Such a compound is water-soluble or water-soluble by partial neutralization with a basic compound, but in order not to impair the water resistance of the formed film, the basic compound may be ammonia and / or the above-mentioned compounds. Must be an organic amine compound. In addition, the compound having a protective colloid function has a number average molecular weight of 1,500 or more so that the effect as a protective colloid can be expressed by adding a small amount and the water resistance and chemical resistance of the formed film are not impaired. It is preferably 2,000 or more, more preferably 2,500 or more.

  The amount of the compound having a protective colloid action is 0.01 to 3% by weight, preferably 0.03 to 2% by weight, based on the polyester resin. If it is this range, stability of the polyester resin water dispersion at the time of an aqueous process and a storage can be improved significantly, without reducing the performance of the film formed. Moreover, the acid value of a polyester resin and content of the said organic solvent can be reduced by using the compound which has this protective colloid effect | action. In addition, the amount used with respect to the polyester resin (A ′) is 0.05% by weight or less, preferably 0.03% by weight or less. The stability of the aqueous dispersion of the polyester resin during the aqueous treatment process and storage can be significantly improved without lowering the water content.

  In the polyester resin used for the resin (a), the acid value is 10 to 40 mgKOH / g, preferably 10 to 35 mgKOH / g. When this acid value exceeds 40 mgKOH / g, the water resistance of the formed film tends to be poor. On the other hand, when the acid value is less than 10 mgKOH / g, the amount of carboxyl groups contributing to the aqueous formation is not sufficient, and there is a tendency that a good aqueous dispersion cannot be obtained. Moreover, the weight average molecular weight measured by GPC (gel permeation chromatography, in terms of polystyrene) is 9,000 or more, or 1% by weight in an equal weight ratio mixed solvent of phenol / 1,1,2,2-tetrachloroethane. It is preferable that the relative viscosity is 1.20 or more when measured at 20 ° C. When the weight average molecular weight is less than 9,000 or the relative viscosity is less than 1.20, there is a tendency that sufficient processability is not imparted to the film formed from the aqueous dispersion of the polyester resin. Furthermore, the weight average molecular weight of the polyester resin is particularly preferably 12,000 or more, more preferably 15,000 or more. The upper limit is preferably 45,000 or less. If it exceeds 45,000, the operability during the production of the polyester resin tends to deteriorate, or the aqueous dispersion using such a polyester resin tends to be too viscous. The relative viscosity is preferably 1.22 or more, more preferably 1.24 or more. The upper limit is preferably 1.95 or less, and if this value is exceeded, the operability during the production of the polyester resin is deteriorated or the viscosity of the aqueous dispersion using such a polyester resin tends to be too high.

In order to sharpen the particle size distribution of the toner, it is necessary to uniformly deposit organic fine particles on the toner surface, and the SP value difference between the resin (a) and the resin (b) is important. The SP value difference between the resin (a) and the resin (b) is preferably 0.1 to 2.3, and more preferably 0.3 to 0.8.
When the difference in SP value between the resin (a) and the resin (b) exceeds 2.3, the toner particle size distribution becomes wide, the image density varies, or the shell becomes a core surface due to long-term stirring in the developing unit. The film may be peeled off from the film, causing filming on the photoconductor and a decrease in fluidity, which may deteriorate charging stability. Further, when the SP value difference between the resin (a) and the resin (b) is less than 0.1, the resin (a) is compatible with the resin (b) and the organic fine particles are taken into the toner, and the toner particle size distribution. May become wide and image density variation may be observed. Furthermore, since the core is exposed, deterioration of charging stability over time due to filming of the core resin to the photoreceptor, deterioration of charging stability against changes in the usage environment such as temperature and humidity, deterioration of heat storage stability It can be caused. Further, the SP value of the resins (a) and (b) is preferably 8 to 35, and if it is outside this range, the granulation property may be deteriorated.

Here, the SP value (solubility parameter / Solubility Parameter) will be described.
The SP value is a so-called solubility parameter, and is a numerical value of how easily each other dissolves.
This SP value is expressed by the square root of the attractive force between molecules, that is, the cohesive energy density (CED).
CED is the amount of energy required to evaporate 1 ml.
Specifically, the calculation of the SP value in the present invention can be performed using the following formula (3) by the Fedors method.
SP value (dissolution parameter) = (CED value) ^1/2 = (E / V) ^1/2 Formula (3)

In the above formula (3), E is the molecular aggregation energy (cal / mol), V is the molecular volume (cm ³ / mol), and the evaporation energy of the atomic group is Δei, and the molar volume is Δvi, It is represented by the following formula (4) and formula (5).
E = ΣΔei (4)
V = ΣΔvi (5)

Although there are various theories on the calculation method of the SP value, the Fedors method generally used in the present invention is used.
For this calculation method and various data of the evaporation energy Δei and molar volume Δvi of each atomic group, “basic theory of adhesion” (written by Imoto Satoshi, published by Kobunshi Shuppankai, Chapter 5) was used as a reference.
For those not shown, such as -CF3 group, R.I. F. Fedors, Polym. Eng. Sci. 14, 147 (1974).
For reference, when the SP value represented by the formula (3) is converted to (J / cm ³ ) 1/2, 2.046 is converted to SI unit (J / m ³ ) 1/2. In that case, 2046 may be multiplied.

In a case where the monomer is added during the polymerization to change the resin skeleton, it is difficult to calculate the SP value from the charged composition ratio.
Further, since the composition of the resin contained in the toner itself is generally unknown, it is difficult to calculate the SP value.
However, the SP value can be calculated by the Fedors method by specifying the type and ratio of the monomer constituting the resin.
Therefore, as will be described in detail later, the SP value can be calculated by performing separation by GPC and adopting the following analysis method for each separated component.

That is, in GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire integral W1 of the elution curve are collected.
After concentrating and drying the collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. From the integration ratio of each element, The constituent monomer ratio can be calculated.
Another method is to calculate the constituent monomer ratio by concentrating the eluate, hydrolyzing with sodium hydroxide, etc., and performing qualitative quantitative analysis of the decomposition products using high performance liquid chromatography (HPLC). Can do.

(Toner component analysis)
The means for analyzing each component in the toner will be described below.
First, 1 g of toner was put into 100 ml of THF to obtain a solution in which soluble components were dissolved while stirring for 30 minutes at 25 ° C.
This was filtered through a membrane filter having an opening of 0.2 μm, and acetone was distilled off to obtain a THF soluble component in the toner.
Next, this was dissolved in THF to prepare a sample for GPC measurement, and injected into the GPC used for the molecular weight measurement of each resin described above.
On the other hand, a fraction collector is arranged at the eluate outlet of GPC, and the eluate is collected every predetermined count, and elution is performed every 5% in area ratio from the start of elution of the elution curve W1 (rise of the curve). A liquid was obtained.
Next, for each elution, 30 mg of sample was dissolved in 1 ml of deuterated chloroform, and tetramethylsilane (TMS) was added as a reference substance at a concentration of 0.05% by volume.
The solution was filled into a 5 mm diameter glass tube for NMR measurement, and a spectrum was obtained by performing integration 128 times at a temperature of 23 to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .
The monomer composition and composition ratio of the resin (a) and the resin (b) contained can be determined from the peak integration ratio of the obtained spectrum.

  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. The volume average particle diameter (Dv) of the resin particles (A) is preferably 0.035 to 0.4 μm. When the volume average particle diameter (Dv) of the resin particles (A) exceeds 0.4 μm, the lower limit of fixing is deteriorated, or the resin particles (A) are easily peeled off from the toner surface, and the film is filmed on the photosensitive member over time. There is a possibility that the chargeability of the battery deteriorates. Further, if the volume average particle diameter (Dv) of the resin particles (A) is less than 0.035 μm, the toner surface is densely covered with resin fine particles, the lower limit of fixing is deteriorated, the heat resistant storage stability is deteriorated, There is a possibility that charging stability with respect to changes in usage environment such as temperature and humidity may deteriorate. 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, 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.

  Although there is no restriction | limiting in particular as a glass transition point (Tg) of resin (a), It is preferable that it is 50 to 100 degreeC, More preferably, it is 55 to 90 degreeC, Most preferably, it is 58 to 75 degreeC. ° C. When the Tg is less than 50 ° C., 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., the resin particles containing the resin (a) may impair the adhesion to the fixing paper, and an increase in the minimum fixing temperature may be observed. 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.

<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 the emulsification 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.
-Halogen-based solvents such as methyl chloride, methyl bromide methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, and perchloroethylene.
-Ester or ester ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate and ethyl cellosolve acetate.
-Ether solvents such as diethyl ether, tetrahydrofuran dioxane, ethyl cellosolve, ptyl cellosolve, propylene glycol monomethyl ether.
-Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone.
-Alcohol solvents, such as methanol ethanol n-propanol isopropanol, n-butanol, isobutanol t-butanol, 2-ethylhexyl alcohol benzyl alcohol.
-Amide solvents such as dimethylformamide dimethylacetamide.
・ Sulphoxide solvents such as dimethyl sulfoxide.
-Heterocyclic compound solvents such as N-methylpyrrolidone.
-A mixture of two or more of the solvents 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) Phthalic acid esters [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate diisodecyl, etc.].
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate and the like].
(V3) Trimellitic acid ester [trimellitic acid tri-2-ethylhexyl, trimellitic acid trioctyl, etc.].
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.].
(V5) Fatty acid ester [butyl oleate and the like].
(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 JP-A-2002-284881 of Patent Document 2, such as 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) And the product 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) and triethanolamine monostearate, stearamide ethyl diethyl methyl ester Such as tertiary inorganic or organic acid salts of amines such as Noruamin the like.

--- 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 compounds represented by the following general formula (1).
[R—NH— (CH ₂ ) _n —COO] _m M—General formula (1)

[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 (1) include alkyl (carbon number 6 to 40) aminopropionic acid type amphoteric surfactants (sodium stearylaminopropionate, sodium laurylaminopropionate, etc.); 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.

  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%. In addition, 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 1.5, more preferably. Is 1.0 to 1.3. If the value of [volume average particle diameter (Dv) / number average particle diameter (Dn)] of the resin particles (C) exceeds 1.5, the toner charge may vary and the image density may become uneven. There is sex. 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 (2) is more preferable. The following general formula (2) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
_{R 1 (OR 2) n OSO} 3 M ··· formula (2)

[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 iron powder (100 emu / g or more) in terms of securing image density 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 member (10)”), a charging roller (20) as a charging unit, Exposure device (30) as exposure means, development device (45) as development means, intermediate transfer member (50), cleaning device (60) as cleaning means having a cleaning blade, and charge removal as charge removal means A lamp (70).

  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 on the inner side and stretch the belt. A part of the three rollers (51) also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member (50). The intermediate transfer member (50) is provided with a cleaning device (90) such as an intermediate transfer member cleaning blade in the vicinity thereof, and a visible image (toner image) is formed on a recording medium (95) such as transfer paper. A transfer roller (80) as a transfer means capable of applying a transfer bias for transferring the toner (secondary transfer) is disposed to face the transfer roller. Around the intermediate transfer member (50), a corona charger (58) for applying a charge to a visible image on the intermediate transfer member (50) is exposed in the rotational direction of the intermediate transfer member (50). It is disposed between the contact portion between the body (10) and the intermediate transfer member (50) and the 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 development unit (45K) includes a developer accommodating portion (42K), a developer supply roller (43K), and a development roller (44K). The yellow developing unit (45Y) includes a developer container (42Y), a developer supply roller (43Y), and a developing roller (44Y). The magenta development unit (45M) includes a developer container (42M), a developer supply roller (43M), and a development 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) uniformly charges the photoconductor (10). An exposure device (30) performs imagewise exposure on the photoreceptor (10) to form an electrostatic latent image. The electrostatic latent image formed on the photoreceptor (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 onto the recording medium (95) such as transfer paper (secondary transfer). Next transfer). As a result, a transfer image is formed on a 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 once removed by the static elimination 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 machine 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 machine 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. An intermediate transfer body cleaning device (17) for removing residual toner on the intermediate transfer body (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) has four image forming units (18) of yellow, cyan, magenta, and black along the conveyance direction. A tandem developing device (120) arranged opposite to each other is arranged. 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), which is an endless belt, is stretched between a pair of rollers (23), and a recording medium (on which the secondary transfer belt (24) is conveyed) The transfer paper) and the 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 in order to form an image on both sides of the transfer paper in the vicinity of the secondary transfer device (22) and the fixing device (25). ) Is arranged.

  Next, full color image formation (color copying) 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 contact glass (32) of the scanner (300) is opened. A document is set on the document and the automatic document feeder (400) is closed.

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32). ) Immediately after the document is set on the scanner (300), 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 read through the imaging lens (35). The color original (color image) is read at (36), and is read as black, yellow, magenta and cyan image information.

Each image information of black, yellow, magenta, and cyan is stored in each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means, And cyan image forming means), and each image forming means forms toner images of black, yellow, magenta, and cyan. That is, each image forming means (18) (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means) in the tandem developing device (120) is as shown in FIG. The photoconductor (10) (black photoconductor (10K), yellow photoconductor (10Y), magenta photoconductor (10M), cyan photoconductor (10C)) and photoconductor (10), respectively. A charging device (160) for uniformly charging, and exposing the photoconductor to each color image-corresponding image based on each color image information (L in FIG. 3), and static images corresponding to each color image on the photoconductor. An exposure device that forms an electrostatic latent image, and the electrostatic latent image is developed with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner. A developing device (61) to be formed, a transfer charger (62) for transferring the toner image onto the intermediate transfer member (50), a cleaning device (63), and a static eliminator (64). Each single-color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this manner are respectively transferred to the black photoconductor (50) on the intermediate transfer member (50) that is rotated by the support rollers (14), (15), and (16). 10K), black image formed on yellow photoconductor (10Y), magenta image formed on magenta photoconductor (10M), and cyan photoconductor (10C). The cyan images thus transferred 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 so that the sheet (recording paper) is fed from one of the paper feed cassettes (144) provided in the paper bank (143). ), Separated one by one by the separation roller (145), sent to the paper feed path (146), and conveyed by the transport roller (147) to the paper feed path (148) in the copying machine main body (150). Guide and stop against the registration roller (49). Alternatively, the sheet feed roller (142) is rotated to feed out the sheets (recording paper) on the manual feed tray (54), separated one by one by the separation roller (145), and put into the manual feed path (53). Stop 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 the intermediate transfer member (50), the secondary transfer device (22), The sheet (recording paper) is sent between the sheets, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device (22). ) A color image is transferred and formed thereon. The residual toner on the intermediate transfer member (50) after the 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 it is synthesized by heat and pressure. A color image (color transfer image) is fixed on a 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), or switched by the switching claw 55 and switched by the sheet reversing device (28). Is reversed and guided to the transfer position again, and after an image is recorded also on the back surface, 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). Including other means as required. In FIG. 4, reference numeral (103) denotes exposure by the exposure means, and reference numeral (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 means (102) while being rotated in the direction of the arrow, and by the exposure means (not shown). By exposure (103), an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing means (104), and the obtained visible image is transferred to the recording medium (105) by the transfer means (108) and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by a 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.

[Production Examples 1 and 2] -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) in Table 1 below were heated and melted at 120 ° C. for 20 minutes, and then 2 parts by mass of tin octylate. The ring-opening polymerization was carried out at 160 ° C. for 3 hours at normal pressure, and further reacted at 130 ° C. for 1 hour at normal pressure. After cooling the taken-out resin to room temperature, it was pulverized into polyester diols (b11-1) to (b11-2) having a polyhydroxycarboxylic acid skeleton. The number average molecular weight Mn of (b11-1) is 3,000, the weight average molecular weight Mw is 5,000, the number average molecular weight Mn of (b11-2) is 3,500, and the weight average molecular weight Mw is It was 5,700. Polyester diols (b12-1) to (b12-2) obtained by dehydrating and condensing raw materials shown in the polyester diol (b12) in Table 1, and the previously obtained polyester diols (b11-1) to (b11- 2) is dissolved in methyl ethyl ketone, followed by adding isophorone diisocyanate (IPDI) as an extender, performing an extension reaction at 50 ° C. for 6 hours, and distilling off the residual lactide and the solvent under reduced pressure. [Resin (b-1) to (b-2)] were obtained. Table 1 shows the number average molecular weight Mn, weight average molecular weight Mw, and SP value of [resins (b-1) to (b-2)].

（表１中、数値は、質量部を示す。）

(In Table 1, numerical values indicate parts by mass.)

[Production Examples 3 to 4] -Production of resins (b-3) to (b-4)-Polyester diols (b11) shown in Table 2 below were placed in an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube. ) Was melted by heating at 120 ° C. for 20 minutes, 2 parts by mass of tin octylate was added, ring-opening polymerization was performed at 160 ° C. for 10 hours at normal pressure, and further reacted at 130 ° C. for 1 hour at normal pressure. . Then, residual lactide was depressurizingly distilled and [resin (b-3)-(b-4)] of manufacture examples 3-4 was obtained. Table 2 shows the number average molecular weight Mn, weight average molecular weight Mw, and SP value of [resins (b-3) to (b-4)].

（表２中、数値は、質量部を示す。）

(In Table 2, numerical values indicate parts by mass.)

[Production Examples 5-6]-Resins (b-5)-(b-6)-
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. Thereafter, residual lactide and caprolactone were distilled off under reduced pressure to obtain [Resin (b-5) to (b-6)] of Production Examples 5 to 6. Table 3 shows the number average molecular weight Mn, weight average molecular weight Mw, and SP value of [resins (b-5) to (b-6)].

（表３中、数値は、質量部を示す。）

(In Table 3, numerical values indicate parts by mass.)

[Production Example 7] -Production of resin (b-7)-
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-7)] of Production Example 7 Got. Table 4 shows the number average molecular weight Mn, weight average molecular weight Mw, and SP value of [resin (b-7)].

（表４中、数値は、質量部を示す。）

(In Table 4, numerical values indicate parts by mass.)

[Production Example 8] 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 9] 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 10] -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-7)] synthesized in Production Examples 1 to 7 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 11 to 20] -Production of first resin (a)-
Esterification reaction by heating a mixture of 1,162 parts by mass of terephthalic acid, 61.2 parts by mass of isophthalic acid, 377 parts by mass of ethylene glycol and 726 parts by mass of neopentyl glycol in an autoclave at 260 ° C. for 2.5 hours. Went. Next, 0.262 parts of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under this condition, the polycondensation reaction was further continued. After 1.5 hours, the system was brought to atmospheric pressure with nitrogen gas, and the temperature of the system was lowered. Mass parts, 365 parts by mass of adipic acid, and 38 parts by mass of trimellitic anhydride were added, and the mixture was stirred at 255 ° C. for 30 minutes and dispensed into a sheet. And after fully cooling to room temperature, this was grind | pulverized with the crusher and the polyester resin of the fraction of 1-6 mm of openings was obtained as [resin (a-1)] using the sieve. Further, polyester resins [resins (a-2) to (a-10)] were obtained in the same manner. The analysis results for each resin are shown in Table 5.

[Production Examples 21 to 42] (Production of fine particle dispersion (w))
In a 2 L glass container with a jacket, 200 parts of resin (a), 35 parts of ethylene glycol mono-n-butyl ether, 0.5 parts by weight of polyvinyl alcohol (Unitika Ltd. “Unitika Poval” 050G) in the number of parts shown in Table 6 below. An aqueous solution (hereinafter referred to as PVA-1) and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 times the total amount of carboxyl groups contained in the polyester resin were introduced, and this was opened in an open system. When stirring at 6,000 rpm using a desktop type homodisper (manufactured by Special Machine Industries Co., Ltd., TK Robotics), no sedimentation of resin particles is observed at the bottom of the container, and it is in a completely floating state. It was confirmed. Therefore, this state was maintained, and hot water was passed through the jacket after 10 minutes for heating. When the temperature in the container reached 68 ° C., the stirring was set at 7,000 rpm, the temperature in the container was kept at 68 to 70 ° C., and the mixture was further stirred for 20 minutes to obtain a milky white uniform aqueous dispersion. Then, cold water was poured into the jacket, cooled to room temperature while stirring at 3500 rpm, and filtered using a stainless steel filter (635 mesh, plain weave). As a result, almost no resin particles remained on the filter. Table 6 shows the analysis results of the obtained filtrate [resin fine particle dispersions (w-1) to (w-22)].

（表６中、数値は、質量部を示す。）

(In Table 6, numerical values indicate parts by mass.)

[Production Examples 43 to 64] -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-22)] produced in Production Examples 21 to 142, respectively, and 0.2 parts by mass of sodium dodecylbenzenesulfonate were mixed. The mixture was uniformly dissolved by stirring to prepare [Aqueous medium phases (1) to (22)]. [Aqueous medium phases (1) to (22)] correspond to those obtained from [fine particle dispersions (w-1) to (w-22)], respectively.

[Production Examples 65-71] -Preparation of resin solution-
[Resin (b-1)-(b-7)], [Polyester prepolymer], and 80 parts by mass of ethyl acetate obtained in Production Examples 1 to 7 in the number of parts shown in Table 7 were added and stirred. Then, [resin solutions (1) to (7)] were prepared. [Resin solutions (1) to (7)] respectively correspond to those obtained from [Resin (b-1) to (b-7)].

（表７中、数値は、質量部を示す。）

(In Table 7, numerical values indicate parts by mass.)

[Production Examples 72 to 78] -Preparation of oil phase-
Next, to each 400 parts by mass of the resin solutions (1) to (7) obtained in Production Examples 65 to 71, carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 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 that 80% by volume of 0.5 mm zirconia beads were filled to obtain [oil phases (1) to (7)]. However, oil phases (1), (2) and (7) were further dissolved by adding 2.5 parts by mass of a ketimine compound to obtain an oil phase. [Oil phases (1) to (7)] correspond to those obtained from [Resin solutions (1) to (7)], respectively.

[Production Example 79] -Preparation of toner base-
Next, 150 parts by mass of each of [Aqueous medium phases (1) to (22)] obtained in Production Examples 43 to 64 is put in another container, and a TK homomixer (manufactured by Special Machine Industries Co., Ltd.) is used. Using, while stirring at 12,000 rpm, 100 parts by mass of [OIL PHASE (1) to (7)] obtained in Production Examples 72 to 78 as shown in Table 7 below was added and mixed for 10 minutes. An emulsified slurry was obtained. Furthermore, 100 parts by mass of each emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min. Got.

[Production of toner base particles]
Next, 100 parts by mass of the dispersion slurry 1 was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, 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. 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 mass parts of 10 mass% hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK type homomixer, the fluorine-type quaternary ammonium salt compound tergent 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. Using a circulating dryer, the obtained filter cake was dried at 40 ° C. for 36 hours, and sieved with a mesh having an opening of 75 μm to prepare toner base particles 1.

  Also, toner bases 2 to 22 were prepared in the same manner as in the production example for preparation of toner base 1. These are shown in Table 8.

[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 of Toner 1]
100 parts by mass of the obtained toner base particles 1 and 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as an external additive were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After 5 cycles of mixing at a speed of 30 m / sec for 30 seconds and resting for 1 minute, the mixture was sieved with a mesh having an opening of 35 μm to prepare toner 1.

[Production of Toner 2]
A toner 2 was produced in the same manner as in Example 1 except that the toner base particles 2 obtained using the dispersion slurry 2 were used in place of the toner base particles 1 in Example 1.

[Preparation of Toner 3]
A toner 3 was produced in the same manner as in Example 1 except that the toner base particles 3 obtained using the dispersion slurry 3 were used in place of the toner base particles 1 in Example 1.

[Preparation of Toner 4]
A toner 4 was produced in the same manner as in Example 1 except that the toner base particles 4 obtained using the dispersion slurry 4 were used in place of the toner base particles 1 in Example 1.

[Preparation of Toner 5]
A toner 5 was produced in the same manner as in Example 1 except that the toner base particles 5 obtained using the dispersion slurry 5 were used in place of the toner base particles 1 in Example 1.

[Preparation of Toner 6]
A toner 6 was produced in the same manner as in Example 1 except that the toner base particles 6 obtained using the dispersion slurry 6 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 7]
A toner 7 was produced in the same manner as in Example 1 except that the toner base particles 7 obtained using the dispersion slurry 7 were used in place of the toner base particles 1 in Example 1.

[Preparation of Toner 8]
A toner 8 was produced in the same manner as in Example 1 except that the toner base particles 8 obtained using the dispersion slurry 8 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 9]
A toner 9 was produced in the same manner as in Example 1 except that the toner base particles 9 obtained using the dispersion slurry 9 were used instead of the toner base particles 1 in Example 1.

[Production of Toner 10]
A toner 10 was produced in the same manner as in Example 1 except that the toner base particles 10 obtained using the dispersion slurry 10 were used instead of the toner base particles 1 in Example 1.

[Production of Toner 11]
A toner 11 was produced in the same manner as in Example 1 except that the toner base particles 11 obtained using the dispersion slurry 11 were used in place of the toner base particles 1 in Example 1.

[Production of Toner 12]
A toner 12 was produced in the same manner as in Example 1 except that the toner base particles 12 obtained using the dispersion slurry 12 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 13]
A toner 13 was produced in the same manner as in Example 1 except that the toner base particles 13 obtained using the dispersion slurry 13 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 14]
A toner 14 was produced in the same manner as in Example 1 except that the toner base particles 14 obtained using the dispersion slurry 14 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 15]
A toner 15 was produced in the same manner as in Example 1 except that the toner base particles 15 obtained using the dispersion slurry 15 were used instead of the toner base particles 1 in Example 1.

[Production of Toner 16]
A toner 16 was produced in the same manner as in Example 1 except that the toner base particles 16 obtained using the dispersion slurry 16 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 17]
A toner 17 was produced in the same manner as in Example 1 except that the toner base particles 17 obtained using the dispersion slurry 17 were used instead of the toner base particles 1 in Example 1.

[Preparation of Toner 18]
A toner 18 was produced in the same manner as in Example 1 except that the toner base particles 18 obtained using the dispersion slurry 18 were used instead of the toner base particles 1 in Example 1.

[Comparative Example 1; -Production of Toner 19-]
A toner 19 was produced in the same manner as in Example 1 except that the toner base particles 19 obtained using the dispersion slurry 19 were used in place of the toner base particles 1 in Example 1.

[Comparative Example 2; -Production of Toner 20-]
A toner 20 was produced in the same manner as in Example 1 except that the toner base particles 20 obtained using the dispersion slurry 20 were used instead of the toner base particles 1 in Example 1.

[Comparative Example 3; -Production of Toner 21-]
A toner 21 was produced in the same manner as in Example 1 except that the toner base particles 21 obtained using the dispersion slurry 21 were used instead of the toner base particles 1 in Example 1.

[Comparative Example 4; -Production of Toner 22]
A toner 22 was produced in the same manner as in Example 1 except that the toner base particles 22 obtained using the dispersion slurry 22 were used instead of the toner base particles 1 in Example 1.

[Preparation of Developer 1]
Developer 1 was prepared by mixing 5 parts by mass of toner 1 and 95 parts by mass of the carrier.

[Preparation of Developer 2]
5 parts by mass of toner 2 and 95 parts by mass of the carrier were mixed to prepare developer 2.

[Preparation of Developer 3]
5 parts by mass of toner 3 and 95 parts by mass of the carrier were mixed to prepare developer 3.

[Preparation of Developer 4]
Developer 4 was prepared by mixing 5 parts by mass of toner 4 and 95 parts by mass of the carrier.

[Preparation of Developer 5]
5 parts by mass of toner 5 and 95 parts by mass of the carrier were mixed to prepare developer 5.

[Preparation of Developer 6]
5 parts by mass of toner 6 and 95 parts by mass of the carrier were mixed to prepare developer 6.

[Preparation of Developer 7]
5 parts by mass of toner 7 and 95 parts by mass of the carrier were mixed to prepare developer 7.

[Preparation of Developer 8]
5 parts by mass of toner 8 and 95 parts by mass of the carrier were mixed to prepare developer 8.

[Preparation of Developer 9]
5 parts by mass of toner 9 and 95 parts by mass of the carrier were mixed to prepare developer 9.

[Preparation of Developer 10]
5 parts by mass of toner 10 and 95 parts by mass of the carrier were mixed to prepare developer 10.

[Preparation of Developer 11]
5 parts by mass of toner 11 and 95 parts by mass of the carrier were mixed to prepare developer 11.

[Preparation of Developer 12]
5 parts by mass of toner 12 and 95 parts by mass of the carrier were mixed to prepare developer 12.

[Preparation of Developer 13]
5 parts by mass of toner 13 and 95 parts by mass of the carrier were mixed to prepare developer 13.

[Preparation of Developer 14]
5 parts by mass of toner 14 and 95 parts by mass of the carrier were mixed to prepare developer 14.

[Preparation of Developer 15]
The developer 15 was prepared by mixing 5 parts by mass of the toner 15 and 95 parts by mass of the carrier.

[Preparation of Developer 16]
5 parts by mass of toner 16 and 95 parts by mass of the carrier were mixed to prepare developer 16.

[Preparation of Developer 17]
5 parts by mass of toner 17 and 95 parts by mass of the carrier were mixed to prepare developer 17.

[Preparation of Developer 18]
5 parts by mass of toner 18 and 95 parts by mass of the carrier were mixed to prepare developer 18.

[Comparative Example 5; -Production of Developer 19]
5 parts by mass of toner 19 and 95 parts by mass of the carrier were mixed to prepare developer 19.

[Comparative Example 6; -Production of Developer 20]
5 parts by mass of toner 20 and 95 parts by mass of the carrier were mixed to prepare developer 20.

[Comparative Example 7; -Production of Developer 21-]
5 parts by mass of toner 21 and 95 parts by mass of the carrier were mixed to prepare developer 21.

[Comparative Example 8; -Preparation of Developer 22-]
5 parts by mass of toner 22 and 95 parts by mass of the carrier were mixed to prepare developer 22.

  Next, the average particle diameter, fixability, heat-resistant storage stability, image density, charging stability with time, and charging environment fluctuation were evaluated using the obtained developers according to the following evaluation methods. The results are shown in Table 9 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. The dispersion process 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 Company) . 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: The lower limit fixing temperature is less than 135 ° C. B: The lower limit fixing temperature is 135 ° C. or more and less than 145 ° C.

<< 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

<< Image density >>
Using a tandem color image forming apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.), the surface temperature of the fixing roller is set to 160 ° C. ± 2 ° C., and toner is applied to the copy paper TYPE 6000 <70 W> (manufactured by Ricoh Co., Ltd.). A solid image having an adhesion amount of 1.00 ± 0.05 mg / cm ² was formed. The image density at any six positions of the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite) to obtain the image density (average value), and the obtained image density ( The average value was evaluated according to the following criteria.
〔Evaluation criteria〕
A: Image density is 2.2 or more B: Image density is 2.0 or more and less than 2.2 C: Image density is 1.70 or more and less than 2.0 D: Image density is less than 1.70

<< Charging stability over time >>
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 the 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

<< Charging environment fluctuation >>
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 variation rate, the more stable the charging property.

  In the above formula (1), [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

  The resin (a) particles composed of a polyester resin are adhered to the surface of the resin (b) containing a polyhydroxycarboxylic acid skeleton, and the SP value difference between the resin (a) and the resin (b) is 0.1-2. It was confirmed that the toner No. 3 has both low-temperature fixability and heat-resistant storage stability, and a toner having a sharp particle size distribution is obtained, and the image density, charging stability with time, and charging environment fluctuation are improved. . On the other hand, the toner having a small difference in SP value between the resin (a) and the resin (b) as in Comparative Example 1 has a wide particle size distribution and greatly deteriorates in heat storage stability, image density, charging stability with time, and charging environment fluctuation. did. This is presumably because the resins (a) and (b) are compatible at the time of granulation and the toner surface is exposed. As in Comparative Examples 2 and 3, the toner having a large SP value difference between the resin (a) and the resin (b) has a wide particle size distribution and deteriorates the image density and charging stability with time. This is presumably because the resin (a) and the resin (b) are incompatible with each other, so that the shell is peeled off by long-term stirring in the developing unit. Further, a toner using a petroleum-based resin as a binder resin as in Comparative Example 4 achieves both low-temperature fixability and heat-resistant storage stability like a toner using a resin containing a polyhydroxycarboxylic acid skeleton as a binder resin. It is not possible.

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 JP 2010-122667 A

Claims (15)

  A toner comprising resin particles (C) having a first resin (a) and resin particles (B) containing a second resin (b), wherein the resin (a) comprises the resin particles It is attached to the surface of (B), the resin (a) is a polyester resin, the resin (b) has an amorphous polyhydroxycarboxylic acid skeleton, and the resin (a) And the resin (b) has a SP value difference of 0.1 to 2.3.   The toner according to claim 1, wherein a difference in SP value between the resin (a) and the resin (b) is 0.3 to 0.8.   The toner according to claim 1, wherein the resin (a) has a volume average particle diameter Dv (a) of 35 nm to 400 nm.   4. The toner according to claim 1, wherein the resin (a) has a glass transition point Tg (a) of 55 to 100 ° C. 5.   The toner according to any one of claims 1 to 4, wherein the resin (a) is a resin having a polyester unit composed of at least a polybasic acid and a polyhydric alcohol. The resin (b) has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and the optical purity X (%) of the resin (b) represented by the following formula (1) is 80% or less. The toner according to claim 1.
Optical purity X (%) = | X (L isomer) −X (D isomer) | 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 claim 1, 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, comprising a resin (b1).   The mass ratio of the polyester diol (b11) having a polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than the polyester diol (b11) is 31:69 to 90:10, The toner described.   The resin (b) contains a linear polyester resin (b1) and a resin (b2) obtained by reacting the precursor (b0). Toner according to.   A developer comprising the toner according to claim 1.   The developer according to claim 12, further comprising a carrier.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to claim 1 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of claims 1 to 11 as the electrostatic latent image. And developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.

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