JP4944549B2 - Toner and image forming method using the same - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an image forming method using the toner.

  In the image formation by electrophotography, generally, an electric latent image is formed on a photoconductor produced using a photoconductive substance by various means. Next, after developing the latent image using a developer, the image formed by the developer is transferred to paper or the like as necessary, and then fixed by heating, pressing, or solvent vapor.

  The methods for developing electrical latent images can be broadly divided into a liquid development method using a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. And other dry development methods using a dry developer in which a colorant such as carbon black is dispersed in a resin (hereinafter also referred to as “toner”). in use.

  As a fixing method in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner at the time of fixing tends to be small. In the 1999 International Energy Agency (IEA) DSM (Demand-Side Management) program, there is a technology procurement project for next-generation copiers, and the required specifications are published. For copiers of 30 cpm or more, the standby time is within 10 seconds, and power consumption during standby is 10 to 30 watts or less (differs depending on the copying speed). Achievement is required. As a method for achieving such a requirement, a method of reducing the heat capacity of a fixing member such as a heating heat roller to improve the temperature responsiveness of the toner can be considered, but it is not fully satisfactory.

In order to achieve the above requirement and minimize the waiting time, it is considered to be an essential technical achievement matter to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.
In order to cope with such low-temperature fixing, attempts have been made to use polyester resins having excellent low-temperature fixability and relatively good heat-preserving stability in place of styrene-acrylic resins that have been widely used (for example, patent documents). 1, Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and Patent Document 6). In addition, for the purpose of improving low-temperature fixability, an attempt to add a specific non-olefinic crystalline polymer to the binder (see Patent Document 7), an attempt to use a crystalline polyester (see Patent Document 8), and the like have been proposed. However, it cannot be said that the molecular structure and molecular weight of the polyester resin are optimized.

  Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of the DSM program, and it is necessary to establish a low-temperature fixing technique that is further advanced from the conventional technical field. Therefore, it is necessary to control the thermal characteristics of the resin itself for further low-temperature fixing. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the molecular weight is reduced. If the F1 / 2 temperature is lowered too much, there is a problem that the hot offset occurrence temperature is lowered. Therefore, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner that has excellent low-temperature fixability and a high hot offset occurrence temperature.

Next, a method for producing a toner used for developing an electrostatic image is roughly classified into a pulverization method and a polymerization method.
In the pulverization method, a colorant, a charge control agent, an offset preventive agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the toner composition obtained is pulverized and classified to produce a toner. ing. According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. That is, the toner composition obtained by melt mixing must be pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and a copy image having good resolution and gradation can be obtained. Therefore, the fine powder having a particle size of 4 μm or less and the coarse powder having a particle size of 15 μm or more must be removed by classification, resulting in a disadvantage that the toner yield becomes 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 it has a disadvantage that it adversely affects the fluidity, developability, durability, image quality, etc. of the toner. There is.

In recent years, in order to overcome these problems in the pulverization method, a toner production method using a polymerization method has been proposed and implemented. For example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (see Patent Document 9).
However, in these toner production methods, it has been difficult to produce toner using a polyester resin superior in low-temperature fixability.
In order to solve this problem, for example, a toner in which a toner containing at least a polyester resin is spheroidized using a solvent in water (see Patent Document 10), a toner using an isocyanate reaction (see Patent Document 11), and the like are proposed. Has been. However, none of these proposals can satisfy the low-temperature fixability and the toner productivity.

  Accordingly, a toner capable of achieving both excellent low-temperature fixability and anti-offset performance, and capable of forming a good high-definition image, and an image forming method using the toner have not yet been obtained. It is the present situation that a safe provision is desired.

JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, an object of the present invention is to provide a toner that can achieve both excellent low-temperature fixability and offset resistance and can form a good high-definition image, and an image forming method using the toner. To do.

Means for solving the problems are as follows. That is,
<1> A toner containing at least two binder resins and a colorant,
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. The toner satisfies 0.
<2> After preparing an oil phase containing a toner material containing at least one binder resin and a colorant, the oil phase is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the aqueous medium A toner containing at least two or more binder resins granulated therein,
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. The toner satisfies 0.
<3> After preparing an oil phase containing a toner material containing at least a binder resin, a binder resin precursor, and a colorant, the oil phase is emulsified or dispersed in an aqueous medium to prepare a dispersion. A toner containing at least two or more binder resins granulated in the aqueous medium,
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. The toner satisfies 0.
<4> After a toner solution containing at least a binder resin, a binder resin precursor, and a colorant is dissolved or dispersed in an organic solvent to prepare a toner solution, the toner solution is emulsified or dispersed in an aqueous medium. A toner containing at least two or more binder resins prepared by preparing a dispersion and granulating in an aqueous medium,
When the solubility parameter of the binder resin in the toner material is Sp1, and the solubility parameter of the binder resin precursor is Sp3, the following equation is satisfied: 0.3 ≦ | Sp1-Sp3 | ≦ 1.0 This is a characteristic toner.
<5> After a toner solution containing at least a binder resin, a binder resin precursor, and a colorant is dissolved or dispersed in an organic solvent to prepare a toner solution, the toner solution is emulsified or dispersed in an aqueous medium. A toner containing at least two or more binder resins prepared by preparing a dispersion and granulating in an aqueous medium,
Assuming that the solubility parameter of one of the two or more types of binder resins in the toner is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 A toner satisfying | ≦ 1.0.
<6> The toner according to any one of <1> to <5>, wherein two or more binder resins have a polyester skeleton.
<7> The above <1> to <6>, wherein one binder resin of two or more kinds of binder resins in the toner is an ethyl acetate-insoluble polyester resin, and the other binder resin is an ethyl acetate-soluble polyester resin. The toner according to any one of the above.
<8> The toner according to <7>, wherein the solubility parameter of the ethyl acetate-insoluble polyester resin is Sp1H and the solubility parameter of the ethyl acetate-soluble polyester resin is Sp1L, and the toner satisfies the following formula, Sp1H> Sp1L.
<9> The toner according to <8>, wherein the following formula, 0.3 ≦ (Sp1H−Sp1L) ≦ 1.0 is satisfied.
<10> The toner according to any one of <3> to <9>, wherein the binder resin precursor is soluble in ethyl acetate.
<11> When the solubility parameter of the binder resin precursor is Sp3 and the solubility parameter of the ethyl acetate-soluble polyester resin is Sp1L, the following formula, Sp3> In any one of the above <7> and <10> satisfying Sp1> Sp1L Toner.
<12> A toner solution was prepared by dissolving or dispersing a toner material containing at least an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an ethyl acetate-soluble polyester resin in an organic solvent. Thereafter, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium. A toner obtained by forming an adhesive substrate into particles,
The polymer contains at least a modified polyester resin, the reaction product of the active hydrogen group-containing compound and the modified polyester resin is an ethyl acetate insoluble polyester resin, the solubility parameter of the ethyl acetate insoluble polyester resin is Sp1H, and the acetic acid When the solubility parameter of the ethyl-soluble polyester resin is Sp1L, the toner satisfies the following formula: 0.3 ≦ (Sp1H−Sp1L) ≦ 1.0.
<13> The toner according to any one of <7> to <12>, wherein the ethyl acetate insoluble polyester resin has a crosslinking point in a molecular chain.
<14> The toner according to any one of <7> to <13>, wherein the ethyl acetate insoluble polyester resin includes a gel component.
<15> The toner according to any one of <12> to <14>, wherein the modified polyester resin contains an isocyanate group.
<16> The toner according to <15>, wherein an isocyanate group content based on JIS K1603 in the modified polyester resin is 2.0% by mass or less.
<17> From <12>, wherein the diol component in the modified polyester resin is at least one selected from 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, and 1,6-hexanediol. The toner according to any one of <16>.
<18> Any one of <1> to <17>, wherein the volume average particle diameter (Dv) is 3 to 8 μm and the volume average particle diameter (Dv) / number average particle diameter (Dn) is 1.25 or less. The toner according to claim 1.
<19> A developer comprising the toner according to any one of <1> to <18>.
<20> A toner-containing container filled with the toner according to any one of <1> to <18>.
<21> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <18> to be a visible image And a developing means for forming the process cartridge.
<22> 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 of <1> to <18> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, and Fixing means for fixing the transferred image transferred to the recording medium And an image forming apparatus characterized by comprising:
<23> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <18> The image forming apparatus includes at least a developing step for developing to form a visible image, a transferring 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 image forming method.

In the first embodiment, the toner of the present invention comprises at least two or more binder resins and a colorant.
Assuming that one of the two or more binder resins has a solubility parameter Sp1, and the other binder resin has a solubility parameter Sp2, the following equation 0.3 ≦ | Sp1-Sp2 | ≦ 1.0 is satisfied.
In the second embodiment, the toner of the present invention is prepared by preparing an oil phase containing a toner material containing at least one binder resin and a colorant, and then emulsifying or dispersing the oil phase in an aqueous medium. Comprising at least two or more binder resins formed by granulation in the aqueous medium,
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. Satisfy 0.
In the third embodiment, the toner of the present invention is prepared by preparing an oil phase containing at least a binder resin, a binder resin precursor, and a toner material containing a colorant, and then emulsifying or dispersing the oil phase in an aqueous medium. Prepared at least two binder resins obtained by granulation in the aqueous medium,
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. Satisfy 0.
In the fourth embodiment, the toner of the present invention is prepared by dissolving or dispersing a toner material containing at least a binder resin, a binder resin precursor, and a colorant in an organic solvent to prepare a toner solution. A dispersion is prepared by emulsifying or dispersing in an aqueous medium, and contains at least two or more binder resins obtained by granulation in the aqueous medium,
When the solubility parameter of the binder resin in the toner material is Sp1, and the solubility parameter of the binder resin precursor is Sp3, the following equation is satisfied: 0.3 ≦ | Sp1-Sp3 | ≦ 1.0.
In the fifth aspect of the toner of the present invention, a toner solution containing at least a binder resin, a binder resin precursor, and a colorant is dissolved or dispersed in an organic solvent to prepare a toner solution. A dispersion is prepared by emulsifying or dispersing in an aqueous medium, and contains at least two or more binder resins obtained by granulation in the aqueous medium,
Assuming that one of the two or more binder resins in the toner has a solubility parameter Sp1, and the other binder resin has a parameter Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1.0 Meet.
In the sixth aspect of the toner of the present invention, a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an ethyl acetate-soluble polyester resin is dissolved or dispersed in an organic solvent. After preparing the toner solution, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and the active hydrogen group-containing compound are reacted in the aqueous medium. It is obtained by reacting with a possible polymer to form an adhesive substrate in the form of particles. The polymer contains at least a modified polyester resin, and a reaction product of an active hydrogen group-containing compound and the modified polyester resin is obtained. It is an ethyl acetate insoluble polyester resin, the solubility parameter of the ethyl acetate insoluble polyester resin is Sp1H, and the solubility parameter of the ethyl acetate soluble polyester resin When SP1L, the following formula, satisfies the 0.3 ≦ (Sp1H-Sp1L) ≦ 1.0.
In the toner of any one of the first to sixth embodiments, the absolute value difference in solubility parameter (Sp value) in two or more binder resins (including the binder resin precursor) in the toner is 0. Since the range of 3 or more and 1.0 or less is satisfied, the two or more kinds of resins show an incompatible or pseudo-incompatible state, and the functions of the two or more kinds of resins can be effectively exhibited. Therefore, it is possible to achieve both excellent low-temperature fixability and anti-offset performance, and a good high-definition image can be formed.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is any one of the first to sixth aspects of the present invention. 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. . In the image forming method, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, both excellent low-temperature fixability and anti-offset performance can be achieved, and a high-quality electrophotographic image can be formed.

  According to the present invention, a conventional problem can be solved, a toner capable of achieving both excellent low-temperature fixability and anti-offset performance, and forming a good high-definition image, and the toner. An image forming method can be provided.

(toner)
In the first embodiment, the toner of the present invention contains at least two or more binder resins and a colorant, and further contains other components as necessary.
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. 0 is satisfied, and 0.4 ≦ | Sp1-Sp2 | ≦ 1.0 is preferable.
In the present invention, | A−B | means the absolute value of the difference between A and B.

In the second embodiment, the toner of the present invention is prepared by preparing an oil phase containing a toner material containing at least one binder resin and a colorant, and then emulsifying or dispersing the oil phase in an aqueous medium. And at least two or more types of binder resins formed by granulation in the aqueous medium and, if necessary, other components.
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. 0 is satisfied, and 0.4 ≦ | Sp1-Sp2 | ≦ 1.0 is preferable.

In the third embodiment, the toner of the present invention is prepared by preparing an oil phase containing at least a binder resin, a binder resin precursor, and a toner material containing a colorant, and then emulsifying or dispersing the oil phase in an aqueous medium. Thus, a dispersion is prepared and contains at least two or more binder resins obtained by granulation in the aqueous medium, and further contains other components as necessary.
Assuming that the solubility parameter of one of the two or more binder resins is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1. 0 is satisfied, and 0.4 ≦ | Sp1-Sp2 | ≦ 1.0 is preferable.

In the fourth embodiment, the toner of the present invention is prepared by dissolving or dispersing a toner material containing at least a binder resin, a binder resin precursor, and a colorant in an organic solvent to prepare a toner solution. A dispersion is prepared by emulsifying or dispersing in an aqueous medium, and contains at least two kinds of binder resins formed by granulation in the aqueous medium, and further contains other components as necessary. It becomes.
When the solubility parameter of the binder resin in the toner material is Sp1, and the solubility parameter of the binder resin precursor is Sp3, the following equation is satisfied: 0.3 ≦ | Sp1-Sp3 | ≦ 1.0, 0 .4 ≦ | Sp1-Sp3 | ≦ 1.0 is preferable.
Here, the binder resin precursor means a precursor constituting the binder resin in the toner after the reaction. The toner material means a material constituting the toner before the binder resin precursor reacts.

In the fifth aspect of the toner of the present invention, a toner solution containing at least a binder resin, a binder resin precursor, and a colorant is dissolved or dispersed in an organic solvent to prepare a toner solution. A dispersion is prepared by emulsifying or dispersing in an aqueous medium, and contains at least two kinds of binder resins formed by granulation in the aqueous medium, and further contains other components as necessary. It becomes.
Assuming that the solubility parameter of one of the two or more types of binder resins in the toner is Sp1, and the solubility parameter of the other binder resin is Sp2, the following equation is given: 0.3 ≦ | Sp1-Sp2 | ≦ 1.0 is satisfied, and 0.4 ≦ | Sp1-Sp2 | ≦ 1.0 is preferable.

  In the sixth aspect of the toner of the present invention, a toner material containing an active hydrogen group-containing compound, a polymer capable of reacting with the active hydrogen group-containing compound, and an ethyl acetate-soluble polyester resin is dissolved or dispersed in an organic solvent. After preparing the toner solution, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and the active hydrogen group-containing compound are reacted in the aqueous medium. It is obtained by reacting with a possible polymer to form an adhesive substrate in the form of particles. The polymer contains at least a modified polyester resin, and a reaction product of an active hydrogen group-containing compound and the modified polyester resin is obtained. It is an ethyl acetate insoluble polyester resin, the solubility parameter of the ethyl acetate insoluble polyester resin is Sp1H, and the solubility parameter of the ethyl acetate soluble polyester resin When SP1L, the following formula, satisfies the 0.3 ≦ (Sp1H-Sp1L) ≦ 1.0, preferably 0.4 ≦ (Sp1H-Sp1L) ≦ 1.0.

  In the toners of the first to sixth embodiments, when the absolute value of the difference between the Sp values (| Sp1-Sp3 |) exceeds 1.0, the domains of two or more binder resins in the toner are large. If the temperature is less than 0.3, two or more types of binder resins are too compatible, and low-temperature fixability is not exhibited. Sometimes.

  Here, the solubility parameter (Sp value) is, for example, the Fedors method using the additivity of atomic groups [Poly. Eng. Sci. , 14 (2) 147 (1974)] or the like. Specifically, the Sp value is the square root of the sum of the molar cohesive energies of each atomic group divided by the volume, shows the polarity per unit volume, and uses the additivity of the atomic group. It is possible to calculate using

The two or more types of binder resins in the toners of the first to fifth embodiments are not particularly limited and can be appropriately selected according to the purpose. In this case, the physical properties are different (for example, a low molecular weight polyester resin and a high molecular weight polyester resin). Moreover, the combination (for example, polyester resin and polyester resin precursor) of resin and this resin precursor is also contained. Further, a combination of a non-modified resin and a modified resin (for example, a non-modified polyester resin and a modified polyester resin) is also included.
Such a binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polystyrene resin, poly-α-stilstyrene resin, styrene-acrylonitrile copolymer, styrene-chlorostyrene Copolymer, Styrene-propylene copolymer, Styrene-butadiene copolymer, Styrene-vinyl chloride copolymer, Styrene-vinyl acetate copolymer, Styrene-maleic acid copolymer, Styrene-acrylic acid ester copolymer Styrene resins such as styrene-methacrylic acid ester copolymer, styrene-α-methyl acrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer (monopolymer or copolymer containing styrene or styrene-substituted product) Polymer), polyester resin, epoxy resin, vinyl chloride resin, rosin Examples thereof include modified maleic acid resin, phenol resin, polyethylene resin, polypropylene resin, petroleum resin, polyurethane resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, and polyvinyl butyrate resin. These can be used alone or in combination of two or more.
Among these, a polyester resin having a polyester skeleton is preferable, and one binder resin of two or more binder resins in the toner is an ethyl acetate insoluble polyester resin, and the other binder resin is an ethyl acetate soluble polyester resin. It is particularly preferred.

The binder resin precursor in the third to fifth embodiments is preferably soluble in ethyl acetate.
Here, in the present invention, the ethyl acetate-insoluble polyester resin, the ethyl acetate-soluble polyester resin, and the binder resin precursor soluble in ethyl acetate or insoluble are 0.5 mass of the polyester resin in ethyl acetate. %, When the transmittance in the visible light region is 99.5% or more, it is soluble, and when the transmittance is less than 99.5%, it is insoluble.

In this case, when the solubility parameter of the ethyl acetate-insoluble polyester resin is Sp1H and the solubility parameter of the ethyl acetate-soluble polyester resin is Sp1L, it is preferable to satisfy the following formula, Sp1H> Sp1L. It is more preferable to satisfy (Sp1H-Sp1L) ≦ 1.0.
Further, when the solubility parameter of the binder resin precursor is Sp3 and the solubility parameter of the ethyl acetate-soluble polyester resin is Sp1L, it is preferable to satisfy the following formula: Sp3> Sp1L.

  The modified polyester resin of the sixth form is obtained by condensation polymerization of an acid component and at least one diol compound selected from an aliphatic diol and an alicyclic diol in the presence of a catalyst.

Examples of the diol compound include 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, and the like. You may use individually by 1 type and may use 2 or more types together.
As the acid component, at least one of terephthalic acid and isophthalic acid is suitable.
As the catalyst, a Ti-based catalyst is preferable, and examples thereof include titanium tetrabutoxide.

  The mixing ratio for the polycondensation reaction between the diol compound and the acid component is not particularly limited and may be appropriately selected depending on the purpose. For example, the hydroxyl group [OH] in the diol compound, The equivalent ratio ([OH] / [COOH]) to the carboxyl group [COOH] in the acid component is usually preferably 2/1 to 1/1, and preferably 1.5 / 1 to 1/1. Is more preferable, and it is especially preferable that it is 1.3 / 1-1.02 / 1.

As the modified polyester resin, an isocyanate group-containing polyester prepolymer A) is particularly preferably mentioned.
There is no restriction | limiting in particular as said isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably, For example, the said acid component, at least 1 selected from aliphatic diol and alicyclic diol Examples thereof include those obtained by reacting a polyester resin obtained by condensation polymerization of a seed diol compound in the presence of a catalyst with polyisocyanate (PIC).

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

  As a mixing ratio when the polyisocyanate (PIC) is reacted with the polyester resin, a mixing equivalent ratio of an isocyanate group [NCO] in the polyisocyanate (PIC) and a hydroxyl group [OH] in the polyester resin ( [NCO] / [OH]) is usually preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and 3/1 to 1.5 / 1. More preferably. When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Fixability may deteriorate.

The isocyanate group content based on JIS K1603 in the modified polyester resin is preferably 2.0% by mass or less, and more preferably 1.0 to 2.0% by mass. When the isocyanate group content exceeds 2.0% by mass, the low-temperature fixing performance may not be exhibited.
Here, the said isocyanate group content rate (NCO%) can be measured by the method based on JISK1603, for example.

The modified polyester resin has a mass average molecular weight of preferably 10,000 to 100,000, and more preferably 10,000 to 50,000. If the mass average molecular weight is less than 10,000, low-temperature fixability may not be exhibited, and if it exceeds 100,000, the viscosity becomes too high and granulation may be difficult.
Here, the mass average molecular weight can be determined as follows by molecular weight distribution measurement by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF).
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weights made by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

10-50 degreeC is preferable and, as for the glass transition temperature (Tg) of the said modified polyester resin, 30-50 degreeC is more preferable.
The hydroxyl value of the modified polyester resin is preferably 30 mgKOH / g or less, and more preferably 10 to 25 mgKOH / g.
The acid value of the modified polyester resin is preferably 0 to 10 mgKOH / g, and more preferably 0 to 5 mgKOH / g.
Here, the acid value and the hydroxyl value can be measured by a method defined in JIS K0070.

  Here, the modified polyester resin is, for example, put a diol compound, an acid component, and a titanium-based catalyst in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and at normal pressure at 230 ° C. for 8 hours. It is obtained by reacting, then reacting under reduced pressure of 10 to 15 mmHg for 5 hours, and further reacting with an isocyanate group-containing compound.

The ethyl acetate insoluble polyester resin preferably has a crosslinking point in the molecular chain from the viewpoint of hot offset resistance. The ethyl acetate insoluble polyester component preferably contains a gel component from the viewpoint of hot offset resistance.
Here, the gel component can be measured, for example, by Soxhlet extraction with an organic solvent.

  Next, the toner material used in the present invention includes, for example, at least an active hydrogen group-containing compound, the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound, and an ethyl acetate-soluble polyester component. It contains at least an adhesive substrate obtained by the reaction, and contains a release agent, a colorant, and, if necessary, other components such as resin fine particles and a charge control agent.

-Adhesive substrate-
The adhesive base material has an adhesive property to a recording medium such as paper, and the active hydrogen group-containing compound, the modified polyester resin which is a polymer capable of reacting with the active hydrogen group-containing compound, and ethyl acetate-soluble polyester It may contain at least an adhesive polymer obtained by reacting components in the aqueous medium, and may further contain a binder resin appropriately selected from known binder resins.

  There is no restriction | limiting in particular as a mass average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 is more preferable. When the mass average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an extender, a crosslinking agent, etc. when the modified polyester resin, which is a polymer that can react with the active hydrogen group-containing compound, undergoes an extension reaction, a crosslinking reaction, etc. in the aqueous medium. To do.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, it is a polymer that can react with the active hydrogen group-containing compound. When the modified polyester resin is the isocyanate group-containing polyester prepolymer (A), the isocyanate group-containing polyester prepolymer (A) can be increased in molecular weight by a reaction such as an extension reaction or a crosslinking reaction. Amines (B) are preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, and the like between the active hydrogen group-containing compound and the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (for example, diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking them (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

--Ethyl acetate soluble polyester component--
There is no restriction | limiting in particular as said ethyl acetate soluble polyester component, According to the objective, it can select suitably, The polycondensate of a polyol (PO) and polycarboxylic acid (PC), etc. are mentioned. The ethyl acetate-soluble polyester component is partially compatible with the ethyl acetate-insoluble polyester component, that is, has a similar structure compatible with each other, such as low-temperature fixability and hot offset resistance. This is preferable.

The mass average molecular weight (Mw) of the ethyl acetate-soluble polyester component is preferably a molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF) of 1,000 to 30,000, preferably 1,500. ~ 15,000 is more preferred. When the mass average molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the mass average molecular weight of less than 1,000 is 8 to 28 masses. % Is preferred. On the other hand, when the mass average molecular weight exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the ethyl acetate-soluble polyester component is preferably 30 to 70 ° C, more preferably 35 to 70 ° C, still more preferably 35 to 50 ° C, and particularly preferably 35 to 45 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
As an acid value of the said ethyl acetate soluble polyester component, 1.0-50.0 mgKOH / g is preferable, 1.0-45.0 mgKOH / g is more preferable, 15.0-45.0 mgKOH / g is still more preferable. . Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the ethyl acetate-soluble polyester component is contained in the toner, the mixing mass ratio between the ethyl acetate-insoluble polyester component and the ethyl acetate-soluble polyester component is preferably 5/95 to 25/75. 90-25 / 75 is more preferable.
When the mixing mass ratio of the ethyl acetate-soluble polyester component exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. May get worse.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments 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, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, 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, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, 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. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the styrene or substituted polymer thereof include polyester resins, polystyrene resins, poly p-chlorostyrene resins, and polyvinyl toluene resins. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. 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. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, Although it can select suitably from well-known things according to the objective, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable. Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is still more preferable. If the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability. If the melting point exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenol-based condensate E-89 (both manufactured by Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.) ), Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (made by Nippon Carlit Co., Ltd.); quinacridone; azo face ; Sulfonic acid group, polymer compounds having a functional group such as a carboxyl group, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or the toner. You may fix to the toner surface after particle manufacture.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. 0.1-10 mass parts is preferable with respect to 0.2-5 mass parts. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Resin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, vinyl resins, polyurethane resins, epoxy resins, and polyester resins are particularly preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer. For example, a styrene- (meth) acrylic ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic ester polymer, Examples thereof include a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.
In addition, as the resin fine particles, a copolymer including a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of methacrylic acid ethylene oxide adduct sulfate (“Eleminol RS— 30 ", manufactured by Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles are not particularly limited and can be obtained by polymerization according to a known method appropriately selected according to the purpose, but it is preferable to obtain the resin fine particles as an aqueous dispersion. As a method for preparing the aqueous dispersion of the resin fine particles, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material, and is selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, (Oligomer etc.) or a solvent solution thereof in the presence of a suitable dispersant, and then dispersed in an aqueous medium, followed by heating or adding a curing agent and curing to produce an aqueous dispersion of resin fine particles. 3) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it must be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). A method in which a suitable emulsifier is dissolved in a solution (which may be liquefied by heating), and then water is added to perform phase inversion emulsification. The resin prepared by any polymerization reaction mode such as condensation polymerization) is pulverized using a fine pulverizer such as a mechanical rotary type or a jet type, and then classified to obtain resin fine particles, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization). A method in which resin fine particles are obtained by spraying a resin solution in which a resin is dissolved in a solvent in a mist, and then the resin fine particles are dispersed in water in the presence of a suitable dispersant. (6) A polymerization reaction (addition polymerization, Ring-opening polymerization, polyaddition, addition The resin prepared by adding a poor solvent to a resin solution prepared by dissolving a resin prepared in a solvent in a solvent, or by cooling a resin solution previously heated and dissolved in a solvent. After the fine particles are precipitated and then the solvent is removed to obtain resin particles, the resin particles are dispersed in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, (Any polymerization reaction mode such as polyaddition, addition condensation, condensation polymerization, etc. may be used) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated. Or a method of removing the solvent by reducing pressure, etc., (8) a resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) In resin solution dissolved in A suitable emulsifier is dissolved in water and then water is added to carry out phase inversion emulsification.

  Examples of the toner include toners produced by a known suspension polymerization method, emulsion aggregation method, emulsion dispersion method, etc., and can react with an active hydrogen group-containing compound and the active hydrogen group-containing compound. The toner material containing the modified polyester resin as a polymer is dissolved in an organic solvent to prepare a toner solution, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. And reacting the active hydrogen group-containing compound with the modified polyester resin, which is a polymer capable of reacting with the active hydrogen group-containing compound, to form an adhesive substrate in the form of particles, and removing the organic solvent. The toner obtained is preferably mentioned.

-Toner solution-
The toner solution can be prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples thereof include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch method, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

As an example of the method for producing the toner, a method for producing the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive substrate into particles, for example, preparation of an aqueous medium phase, preparation of the toner solution, preparation of the dispersion, addition of the aqueous medium, etc. Synthesis of the modified polyester resin (prepolymer), which is a polymer that can react with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, and the like are performed.

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The toner solution is prepared by mixing, in the organic solvent, the active hydrogen group-containing compound, the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound, the colorant, the release agent, and the charging agent. It can be carried out by dissolving or dispersing toner materials such as a control agent and the ethyl acetate-soluble polyester component.
In the toner material, components other than the modified polyester resin (prepolymer), which is a polymer capable of reacting with the active hydrogen group-containing compound, are used in the aqueous medium phase preparation, and the resin fine particles are used as the aqueous medium. When dispersed in the aqueous medium, it may be added and mixed in the aqueous medium, or when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

  The dispersion can be prepared by emulsifying or dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification or dispersion, when the active hydrogen group-containing compound and the modified polyester resin that is a polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction, the adhesive base material becomes Generate. The adhesive substrate (for example, the urea-modified polyester resin) is, for example, (1) the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (a) that is a polymer that can react with the active hydrogen group-containing compound. The toner solution containing A)) is emulsified or dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and in the aqueous medium phase (2) The toner solution is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion. Or may be produced by subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium phase, or (3) adding the toner solution to the aqueous medium. After engaged, adding the active hydrogen group-containing compound, to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  Reaction conditions for producing the adhesive substrate by the emulsification or dispersion are not particularly limited, and the modified polyester resin that is a polymer that can react with the active hydrogen group-containing compound and the active hydrogen group-containing The reaction time can be appropriately selected according to the combination with the compound, and the reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. As reaction temperature, 0-150 degreeC is preferable and 40-98 degreeC is more preferable.

  A method of stably forming the dispersion containing the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (A)) which is a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium phase. For example, in the aqueous medium phase, the modified polyester resin (for example, the isocyanate group-containing polyester prepolymer (A)), which is a polymer that can react with the active hydrogen group-containing compound, the colorant, Examples include a method of adding the toner solution prepared by dissolving or dispersing the toner material such as a release agent, the charge control agent, and the ethyl acetate-soluble polyester component in the organic solvent, and dispersing the resultant by shearing force. It is done. The details of the dispersion method are as described above.

  In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets composed of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred. There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like.
Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, and S-113 (all manufactured by Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC- 98, FC-129 (both manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (both manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F -191, F-812, F-833 (all manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 ( All of them are manufactured by Tochem Products Co., Ltd.); .

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group and perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 (both manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (produced by Tochem Products Co., Ltd.); It is done.

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The toner preferably has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), glass transition temperature (Tg), and the like.

The volume average particle diameter (Dv) of the toner is, for example, preferably 3 to 8 μm, more preferably 4 to 7 μm, and still more preferably 5 to 6 μm. Here, the volume average particle diameter is defined as Dv = [Σ (nD ³ ) / Σn] ^1/3 (where n is the number of particles and D is the particle diameter).
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of the agent, toner filming on the developing roller and toner thinning are likely to cause toner fusion to a member such as a blade. On the other hand, when the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and the fluctuation of the toner particle diameter increases when the balance of the toner in the developer is performed. Sometimes.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is preferably 1.25 or less, more preferably 1.05 to 1.25.
In general, it is said that the smaller the toner particle size, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention. On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
On the other hand, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner is not sufficiently charged. It has become clear that there is a case where the cleaning property is deteriorated.

  The volume average particle size (Dv) and the ratio of the volume average particle size to the number average particle size (Dv / Dn) are, for example, a particle size measuring device (“Coulter Counter TAII”, manufactured by Coulter Electronics Co., Ltd.). ) Using an analysis software (Beckman Coulter Multisizer 3 Version 3.51) and measuring with an aperture diameter of 100 μm.

The glass transition temperature of the toner is preferably 40 to 70 ° C. If the glass transition temperature is less than 40 ° C, the heat-resistant storage stability may be insufficient, and if it exceeds 70 ° C, the low-temperature fixability may be adversely affected.
Here, the glass transition temperature of the toner can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

  The coloration of the toner is not particularly limited and can be appropriately selected according to the purpose, and can 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 the colorant, and is preferably a color toner.

<Developer>
The developer used in the present invention contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

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

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is 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 (volume average particle diameter (D ₅₀ )) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer 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. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a 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, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said 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 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. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes too thick. As a result, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
In general, the mixing ratio of the toner and carrier of the two-component developer is preferably 1 to 10.0 parts by mass of toner with respect to 100 parts by mass of carrier.

Since the developer contains the toner of the present invention, it is possible to prevent the formation of photoconductor filming and to stably form an excellent clear high-quality image without fluctuations in image unevenness. .
The developer used in the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for a process cartridge, an image forming apparatus, and an image forming method.

<Toner container>
The toner-containing container used in the present invention contains the toner or developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral unevenness is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container main body is not particularly limited and may be appropriately selected depending on the intended purpose. However, a material having good dimensional accuracy is preferable, for example, a resin is preferable. Among these, for example, polyester Preferred examples include resins, polyethylene resins, polypropylene resins, polystyrene resins, polyvinyl chloride resins, polyacryl resins, polycarbonate resins, ABS resins, polyacetal resins, and the like.
The container containing toner is easy to store, transport, etc., has excellent handleability, and can be suitably used for replenishing toner by being detachably attached to a process cartridge, an image forming apparatus, etc. of the present invention described later. .

<Process cartridge>
The process cartridge used in the present invention can develop an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer. A developing unit that forms a visual image, and further includes other units such as a charging unit, a transfer unit, a cleaning unit, and a discharging unit, which are appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer carried on the surface of the developer carrying member.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, facsimiles, and printers, and is preferably provided detachably in an image forming apparatus described later.

  Here, for example, as shown in FIG. 1, the process cartridge includes an electrostatic latent image carrier (photosensitive drum) 101, a charging device 102, a developing unit 104, and a cleaning unit 107. Furthermore, it has other means as needed. Reference numeral 103 denotes exposure by an exposure apparatus, 105 denotes a recording medium, and 108 denotes a transfer unit.

  Next, an image forming process using the process cartridge shown in FIG. 1 will be described. The photosensitive drum 101 as an electrostatic latent image carrier is rotated in the direction of the arrow while being charged by the charging device 102 and exposed to light 103 by an exposure device (not shown). Is formed. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photosensitive drum after the transfer is cleaned by the cleaning means 107, further neutralized by the neutralizing means (not shown), and the above operation is repeated again.

  As an image forming apparatus used in the present invention, the electrostatic latent image carrier and components such as a developing device and a cleaning device are integrally combined as a process cartridge, and this unit is attached to and detached from the apparatus main body. You may comprise. Further, at least one selected from a charging device, a developing device, a transfer device, a separation device, and a cleaning device is integrally supported together with an electrostatic latent image carrier to form a process cartridge, and is detachably attached to the apparatus main body. One unit may be configured to be detachable using guide means such as a rail of the apparatus main body.

(Image forming apparatus and image forming method)
The image forming apparatus used in 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. Other selected means include, for example, a static elimination means, a cleaning means, a recycling means, a control means, and the like.
The image forming method of 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, a cleaning step. , Including recycling process, control process, etc.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-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.
The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected depending on the purpose. Examples of the shape include a drum shape and a sheet. And endless belts. The structure may be a single-layer structure or a laminated structure, and the size may be appropriately selected according to the size and specifications of the image forming apparatus. Examples of the material include inorganic photoreceptors such as amorphous silicon, selenium, CdS, and ZnO; organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like.

  For example, the amorphous silicon photosensitive member is heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, a thermal CVD method, a photo CVD method, a plasma CVD method, or the like is applied on the support. A photosensitive layer made of a-Si is formed by a film forming method. Among these, the plasma CVD method is particularly preferable, and specifically, a method in which the source gas is decomposed by direct current, high frequency, or microwave glow discharge to form a photosensitive layer made of a-Si on the support is preferable. .

The organic photoreceptor (OPC) has (1) optical characteristics such as a wide light absorption wavelength range and a large amount of light absorption, (2) electrical characteristics such as high sensitivity and stable charging characteristics, (3) In general, it is widely applied because of the wide selection range of materials, (4) ease of production, (5) low cost, and (6) non-toxicity. The layer structure of such an organic photoreceptor is roughly classified into a single layer structure and a laminated structure.
The single-layered photoreceptor has a support and a single-layer type photosensitive layer provided on the support, and further includes a protective layer, an intermediate layer, and other layers as necessary.
The laminated structure of the photoreceptor comprises a support, and a laminate type photosensitive layer having at least a charge generation layer and a charge transport layer in this order on the support, and further includes a protective layer and an intermediate layer as necessary. And other layers.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do.
The electrostatic latent image forming means includes 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. .

  The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger. The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the image forming apparatus. The magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a nonmagnetic conductive sleeve for supporting it, and a magnet roll included therein. When using a magnetic brush, for example, as the material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. , Make it a charger by sticking.
The charger is not limited to the contact charger as described above. However, since an image forming apparatus in which ozone generated from the charger is reduced is obtained, a contact charger is used. preferable.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, 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 can be used.
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 developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit. The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or 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 agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.

There is no restriction | limiting in particular as said intermediate transfer body, According to the objective, it can select suitably from well-known transfer bodies, For example, a transfer belt, a transfer roller, etc. are mentioned suitably.
The static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably several Ωcm or more and 10 ³ Ωcm or less. Thus, by setting the volume resistance of the intermediate transfer member to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Therefore, transfer unevenness during secondary transfer can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

There is no restriction | limiting in particular as a material of the said intermediate transfer body, Although it can select suitably according to the objective from well-known materials, the following are suitable.
(1) A material having a high Young's modulus (tensile modulus) is used as a single layer belt. For example, PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) and PAT (Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) and PC blend material, ETFE and PAT blend material, PC and PAT blend material, thermosetting of carbon black dispersion Examples thereof include polyimide. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and rib displacement is unlikely to occur particularly during color image formation.
(2) A belt having a two- to three-layer structure in which a belt having a high Young's modulus (1) is used as a base layer and a surface layer or an intermediate layer is formed on the outer periphery thereof. It has a performance capable of preventing the line image from being lost due to the hardness of the single layer belt.
(3) An elastic belt having a relatively low Young's modulus using resin, rubber, or elastomer, and such an elastic belt has an advantage that almost no void in a line image occurs due to its softness. In addition, the elastic belt is wider than the drive roll and tension roll, and the elasticity of the belt ears protruding from the roll can be used to prevent meandering, thus reducing costs without requiring ribs or meandering prevention devices. it can.
Among these, the elastic belt (3) is particularly preferable.
The elastic belt is deformed corresponding to a toner layer and a recording medium having poor smoothness in the transfer portion. In other words, since the elastic belt deforms following the local unevenness, good adhesion can be obtained without excessively increasing the transfer pressure with respect to the toner layer, there is no void in characters, and flatness is poor. A transfer image with excellent uniformity can be obtained even on a recording medium.

  There is no restriction | limiting in particular as resin used for the said elastic belt, Although it can select suitably according to the objective, For example, polycarbonate resin, fluororesin (ETFE, PVDF), polystyrene resin, chloropolystyrene resin, poly-alpha -Methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-acrylic) Acid methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester copolymer Polymer (eg, styrene-methyl methacrylate copolymer) Styrene resins such as styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylate copolymer, etc. Or a styrene-substituted monopolymer or copolymer), methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified) Acrylic resin, acrylic-urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, polyethylene resin, polypropylene Resin, polybutadiene Emissions, polyvinylidene chloride resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene - ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide resin and modified polyphenylene oxide resins. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as rubber | gum used for the said elastic belt, According to the objective, it can select suitably, For example, natural rubber, butyl rubber, fluorine-type rubber, acrylic rubber, EPDM rubber, NBR rubber, acrylonitrile-butadiene-styrene rubber , Isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydride Examples thereof include phosphorus rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as an elastomer used for the said elastic belt, According to the objective, it can select suitably, For example, a polystyrene-type thermoplastic elastomer, a polyolefin-type thermoplastic elastomer, a polyvinyl chloride-type thermoplastic elastomer, a polyurethane-type thermoplasticity Examples thereof include elastomers, polyamide-based thermoplastic elastomers, polyurea thermoplastic elastomers, polyester-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers. These may be used individually by 1 type and may use 2 or more types together.

  The conductive agent for adjusting the resistance value used in the elastic belt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal powder such as carbon black, graphite, aluminum, nickel; tin oxide, titanium oxide And conductive metal oxides such as antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxide (ATO), and indium oxide-tin oxide composite oxide (ITO). The conductive metal oxide may be coated with insulating fine particles such as barium sulfate, magnesium silicate, and calcium carbonate.

  In addition, the surface layer of the elastic belt prevents contamination of the electrostatic latent image carrier by the elastic material, reduces the frictional resistance of the belt surface, reduces the adhesion of the toner, and improves the cleaning property and the secondary transfer property. What can do is preferable. The surface layer is made of, for example, a binder resin such as a polyurethane resin, a polyester resin, or an epoxy resin, and a material capable of increasing the lubricity by reducing the surface energy, such as a fluororesin, a fluorine compound, a fluorocarbon, titanium dioxide, a silicon car It is preferable to contain powder or particles such as bites. Further, it is possible to use a material having a reduced surface energy by forming a fluorine-rich surface layer by heat treatment, such as a fluorine-based rubber material.

  There is no restriction | limiting in particular as a manufacturing method of the said elastic belt, Although it can select suitably according to the objective, For example, (1) Centrifugal molding method which pours material into a rotating cylindrical type | mold and forms a belt, ( 2) Spray coating method to form a film by spraying a liquid paint, (3) Dipping method in which a cylindrical mold is dipped in a solution of the material, and (4) Casting to be injected into an inner mold or an outer mold And (5) a method in which a compound is wound around a cylindrical mold and vulcanized and polished.

The method for preventing the elastic belt from stretching is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a method of adding a material for preventing elongation to the core layer, 2) A method of forming a rubber layer on a core layer with little elongation, and the like.
There is no restriction | limiting in particular as a material which prevents the said elongation, Although it can select suitably according to the objective, For example, natural fibers, such as cotton and silk; Polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol Synthetic fibers such as fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers; inorganic fibers such as carbon fibers, glass fibers, boron fibers; iron fibers, copper fibers, etc. A metal fiber etc. are mentioned, What made these materials into the shape of a woven fabric or a thread form is used suitably.

The method for forming the core layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) a woven fabric woven in a cylindrical shape is covered with a mold or the like and coated thereon (2) A method of providing a coating layer on one or both sides of the core layer by immersing a woven fabric woven in a cylindrical shape into liquid rubber, etc. For example, a method of winding in a spiral shape and providing a coating layer thereon may be used.
The thickness of the coating layer depends on the hardness of the coating layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur on the surface layer. Further, since the amount of expansion / contraction increases and the expansion and contraction of the image increase, it is not preferable that the thickness is too large (about 1 mm or more).

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. 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.
The recording medium is typically plain paper, but is not particularly limited as long as an unfixed image after development can be transferred, and can be appropriately selected according to the purpose. A PET base for OHP Etc. can also be used.

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. 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 heating in the heating and pressing 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 in place of the fixing step and the fixing unit depending on the purpose.

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 neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

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

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

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  Next, one mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing unit. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and the transfer means capable of applying a transfer bias for transferring (secondary transfer) a transfer image to the recording medium 95. The transfer roller 80 is arranged so as to be opposed. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 and the intermediate transfer member in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion with the body 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred (secondary transfer) onto the recording medium 95. As a result, a transfer image is formed on the recording medium 95. The residual toner on the electrostatic latent image carrier 10 is removed by the cleaning device 60, and the charge on the electrostatic latent image carrier 10 is once removed by the static elimination lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, and a magenta around the electrostatic latent image carrier 10. Except that the developing unit 45M and the cyan developing unit 45C are directly opposed to each other, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Next, a tandem type image forming apparatus that performs the image forming method of the present invention using the image forming apparatus of the present invention will be described.
The tandem type image forming apparatus has a plurality of image forming elements including at least an electrostatic latent image carrier, a charging unit, a developing unit, and a transfer unit. In this tandem type image forming apparatus, four image forming elements for yellow, magenta, cyan, and black are mounted, and each visible image is created in parallel with the four image forming elements, and is recorded on a recording medium or an intermediate transfer member. Therefore, a full color image can be formed at a higher speed.

  As the tandem type image forming apparatus, (1) as shown in FIG. 4, the surface moves so as to pass through a transfer position that is a region facing each electrostatic latent image carrier 1 of a plurality of image forming elements. A direct transfer method in which a visible image formed on each electrostatic latent image carrier 1 is sequentially transferred to the recording medium S to be transferred by the transfer means 2, and (2) a plurality of images as shown in FIG. The visible image on each electrostatic latent image carrier 1 of the forming element is once transferred sequentially to the intermediate transfer body 4 by the transfer means (primary transfer means) 2, and then the image on the intermediate transfer body 4 is transferred to the secondary transfer means 5. There is an indirect transfer method in which the image is transferred to the recording medium S at once. In FIG. 5, a transfer conveyance belt is used as the secondary transfer unit, but a roller shape may be used.

Comparing the direct transfer method (1) and the indirect transfer method (2), the direct transfer method (1) is a tandem type image forming unit T in which the electrostatic latent image carriers 1 are arranged. The sheet feeding device 6 must be disposed on the upstream side, and the fixing device 7 as a fixing unit must be disposed on the downstream side, which increases the size in the recording medium conveyance direction. On the other hand, in the indirect transfer method (2), the secondary transfer position can be set relatively freely, and the paper feeding device 6 and the fixing device 7 are arranged so as to overlap the tandem type image forming unit T. There is an advantage that downsizing is possible.
In the direct transfer method (1), the fixing device 7 is disposed close to the tandem image forming unit T in order not to increase the size in the recording medium conveyance direction. Therefore, the fixing device 7 cannot be disposed with a sufficient margin that the recording medium S can bend, and an impact when the leading end of the recording medium S enters the fixing device 7 (particularly with a thick recording medium). In addition, the fixing device 7 tends to affect upstream image formation due to the speed difference between the recording medium conveyance speed when passing through the fixing device 7 and the recording medium conveyance speed by the transfer conveyance belt. On the other hand, in the indirect transfer method (2), the fixing device 7 can be arranged with a sufficient margin that the recording medium S can be bent, and therefore the fixing device 7 hardly affects the image formation.
For these reasons, indirect transfer systems have recently attracted attention. In this type of color image forming apparatus, as shown in FIG. 5, the transfer residual toner remaining on the electrostatic latent image carrier 1 after the primary transfer is removed by a cleaning device 8 as a cleaning means, and the electrostatic latent image is thus removed. The surface of the carrier 1 is cleaned to prepare for the image formation again. Further, the transfer residual toner remaining on the intermediate transfer body 4 after the secondary transfer is removed by the intermediate transfer body cleaning device 9 to clean the surface of the intermediate transfer body 4 to prepare for image formation again.

The tandem image forming apparatus shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 6. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording medium conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
In the vicinity of the secondary transfer device 22 and the fixing device 25, a sheet reversing device 28 for reversing the recording medium in order to form an image on both sides of the recording medium is disposed.

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

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

  The black, yellow, magenta, and cyan image information is obtained from each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image forming unit) in the tandem developing device 120. Each image forming unit forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is respectively shown in FIG. Electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The charging device 160 for uniformly charging the electrostatic latent image carrier, and exposing the electrostatic latent image carrier for each color image based on each color image information (L in FIG. 7). An exposure device (not shown) for forming an electrostatic latent image corresponding to each color image on the photoconductor, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) on the electrostatic latent image. Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a charge eliminating device 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on the body 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording medium from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the recording medium on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual sheet feed path 53, and abutted against the registration roller 49 and stopped. 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 time with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and the recording medium is sent between the intermediate transfer member 50 and the secondary transfer device 22. Then, by transferring (secondary transfer) the composite color image (color transfer image) onto the recording medium by the secondary transfer device 22, a color image is transferred and formed on the recording medium. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

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

  In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention that can achieve both excellent low-temperature fixability and offset resistance performance is used, high-quality images can be efficiently formed.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples, “part” and “%” are based on mass unless otherwise specified.
In the following examples and comparative examples, volume average particle size (Dv) and particle size distribution (Dv / Dn), mass average molecular weight, isocyanate group content (NCO%), acid value, hydroxyl value, and glass transition temperature (Tg) The measurement of was performed as follows.

<Measurement of Volume Average Particle Size (Dv) and Particle Size Distribution (Dv / Dn) of Toner>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Coulter Counter TAII”, manufactured by Coulter Electronics Co., Ltd.) with an aperture diameter of 100 μm, and analysis software (Beckman Coulter Multisizer) 3 Version 3.51). Specifically, 0.5 ml of 10% surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker, 0.5 g of each toner is added, Stir with spatula. Next, 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size. From these results, (volume average particle diameter / number average particle diameter) was calculated.

<Measurement of mass average molecular weight>
The mass average molecular weight of the polyester resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05 to 0.6% was injected.
From the molecular weight distribution of the polyester resin measured under the above conditions, the weight average molecular weight of the polyester resin was calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. In the case of an isocyanate terminal-modified polyester resin, a sample in which n-dibutylamine in an amount 3 times the amount of isocyanate groups present in the polyester resin was added and the isocyanate terminal was sealed was used.

<Measurement of isocyanate group content (NCO%)>
NCO% was measured by a method based on JIS K1603. Specifically, after precisely weighing 2 g of the modified polyester, 5 ml of dry toluene is quickly added to completely dissolve the sample. Thereafter, 5 ml of a 0.1 M n-dibutylamine / toluene solution was added using a pipette, and then gently stirred for 15 minutes. Subsequently, 5 ml of isopropanol was added and stirred, and potentiometric titration was performed using a 0.1 M ethanolic hydrochloric acid standard solution. From the obtained titration value, the amount of dibutylamine consumed was calculated, and the isocyanate group content was calculated.

<Method for measuring acid value and hydroxyl value>
The acid value (AV) and hydroxyl value (OHV) were determined by the following procedure. When the sample did not dissolve, a solvent such as dioxane or THF was used as the solvent.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: A mixed solvent of 120 ml of toluene and 30 ml of ethanol was used.
・ Measurement temperature: 23 ℃
Specific measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
The acid value was measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for 10 hours. Furthermore, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated with the above-described apparatus. Specifically, the measurement was performed as follows.
Titration was carried out in advance using standardized N / 10 caustic potassium to alcohol solution, and the acid value was determined from the consumption amount of the alcohol potassium solution by the following formula.
Acid value = KOH (ml number) × N × 56.1 / sample mass where N is a factor of (N / 10) KOH.

-Measurement method of hydroxyl value-
0.5 g of the sample was precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent was correctly added thereto. Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C. After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent. This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JIS K0070-1966).

<Glass transition temperature (Tg)>
A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used as an apparatus for measuring the glass transition temperature (Tg) of the polyester resin.
First, 10 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the heating rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at / min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

Example 1
-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion was obtained. This was designated as [fine particle dispersion 1].
The volume average particle diameter of the fine particles contained in the obtained [fine particle dispersion 1] was measured with a particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. there were. Further, a part of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the mass average molecular weight was 150,000.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

-Synthesis of low molecular weight polyester-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid, and 2 parts of dibutyltin oxide was charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put into a reaction vessel, and reacted at 180 ° C. for 2 hours under normal pressure to synthesize [low molecular weight polyester 1].
The obtained [low molecular weight polyester 1] had a glass transition temperature (Tg) of 43 ° C., a mass average molecular weight (Mw) of 6,700, a number average molecular weight of 2,500, and an acid value of 25 mgKOH / g.

-Preparation of masterbatch (MB)-
1,200 parts of water, 540 parts of carbon black (Printex35, manufactured by Degussa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 1,200 parts of polyester resin (manufactured by Sanyo Chemical Industries, RS801) In addition, it was mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch. This is designated as [Masterbatch 1].

-Synthesis of Prepolymer 1-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. Then, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to synthesize [Intermediate Polyester 1].
The obtained [Intermediate polyester 1] had a mass average molecular weight of 28,000, a glass transition temperature (Tg) of 36 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 16.5 mgKOH / g.
Next, 250 parts of the [intermediate polyester 1], 18 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and are heated at 100 ° C. for 5 hours. Reaction was performed to synthesize [Prepolymer 1].
The isocyanate mass% of the obtained [Prepolymer 1] was 1.18% .

-Preparation of oil phase-
In a reaction vessel equipped with a stirrer and a thermometer, 378 parts of [Low molecular polyester 1], 110 parts of carnauba wax, 22 parts of charge control agent (CCA; salicylic acid metal complex E-84, manufactured by Orient Chemical Industry Co., Ltd.) , And 947 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, the temperature was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to prepare a dissolved product. This is referred to as [Raw material solution 1].
Next, 1,324 parts of [Raw Material Solution 1] was transferred into the reaction vessel, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed: 1 kg / hr, disk peripheral speed: 6 m / second, Carbon black and wax were dispersed under the conditions of 0.5 mm zirconia bead filling amount: 80% by volume and number of passes: 3 times. Next, 1,324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and a dispersion was obtained using a bead mill under the same conditions as described above, with the number of passes being one time. This is designated as [Pigment and Wax Dispersion 1]. The obtained [Pigment and Wax Dispersion 1] had a solid content concentration (130 ° C., 30 minutes) of 50%.

-Emulsification-
[Pigment and wax dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and isophoronediamine 1.3 parts are put in a container, and 5,000 rpm using a TK homomixer (made by Tokushu Kika Co., Ltd.). Mix for 1 minute. Thereafter, 1,200 parts of [Aqueous Phase 1] was added to the reaction vessel and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain an aqueous medium dispersion. This is designated as [Emulsified slurry 1].

-Deorganic solvent-
[Emulsion slurry 1] is put into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging is performed at 45 ° C. for 4 hours, and the organic solvent is distilled off. A dispersion was obtained. This is designated as [Dispersion Slurry 1].
The obtained [Dispersion Slurry 1] had a volume average particle size of 5.13 μm and a number average particle size of 4.51 μm as measured using Coulter Multisizer II (manufactured by Nikka Machine Co., Ltd.).

-Cleaning and drying-
[Dispersion Slurry 1] 100 parts were filtered under reduced pressure, and then washed and dried as follows.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2) 100 parts of distilled water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake of (3) and mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered twice to obtain a filter cake.
The obtained filter cake was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh of 75 μm to obtain a toner. This is referred to as [Toner 1].

(Example 2)
-Production of Toner 2-
[Toner 2] was produced in the same manner as in Example 1 except that [Low molecular polyester 1] was used instead of [Low molecular polyester 1] in Example 1.

-Synthesis of low molecular weight polyester 2-
Place 712 parts of bisphenol A ethylene oxide 2-mole adduct, 208 parts of isophthalic acid, 46 parts of adipic acid, and 2 parts of a titanium catalyst in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, under normal pressure. , Reacted at 230 ° C. for 8 hours. Next, after 5 hours of reaction at 10 to 15 mmHg, 44 parts of trimellitic anhydride was placed in the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize [low molecular weight polyester 2].
The obtained [Low molecular weight polyester 2] had a mass average molecular weight of 5,500, a glass transition temperature (Tg) of 45 ° C., and an acid value of 25 mgKOH / g.

(Example 3)
-Production of Toner 3-
In Example 2, instead of [Prepolymer 1], [Prepolymer 2] synthesized as follows was used, except that 1.3 parts of isophoronediamine was changed to 1.2 parts. Thus, [Toner 3] was produced.

-Synthesis of Prepolymer 2-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 428 parts of ethylene glycol, 745 parts of terephthalic acid, 109 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. The mixture was reacted for 8 hours, and then reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize [Intermediate Polyester 2].
The obtained [Intermediate polyester 2] had a mass average molecular weight of 31,000, a glass transition temperature (Tg) of 38 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 15.8 mgKOH / g.
Next, 250 parts of the [intermediate polyester 2], 17.2 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe at 100 ° C. By reacting for 5 hours, [Prepolymer 2] was synthesized.
The isocyanate mass% of the obtained [Prepolymer 2] was 1.12% .

Example 4
-Production of Toner 4-
[Toner 4] was produced in the same manner as in Example 2 except that [Prepolymer 3] synthesized as follows was used instead of [Prepolymer 1] in Example 2.

-Synthesis of Prepolymer 3-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 537 parts of neopentyl glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide are placed at 230 ° C. under normal pressure. Was reacted for 8 hours under reduced pressure of 10 to 15 mmHg to synthesize [Intermediate Polyester 3].
The obtained [Intermediate Polyester 3] had a weight average molecular weight = 28,000, a glass transition temperature (Tg) = 34 ° C., an acid value = 0.5 mgKOH / g, and a hydroxyl value = 16.3 mgKOH / g.
Next, 250 parts of the [intermediate polyester 3], 17.7 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe at 100 ° C. By reacting for 5 hours, [Prepolymer 3] was synthesized. The isocyanate mass% of the obtained [Prepolymer 3] was 1.16% .

(Example 5)
-Production of Toner 5-
[Toner 5] was produced in the same manner as in Example 2 except that [Prepolymer 4] synthesized as follows was used instead of [Prepolymer 1] in Example 2.

-Synthesis of Prepolymer 4-
Place 623 parts of 1,6-hexanediol, 570 parts of terephthalic acid, 83 parts of trimellitic anhydride, and 2 parts of titanium tetrabutoxide in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, under normal pressure. The reaction was carried out at 230 ° C. for 8 hours, and then under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize [Intermediate polyester 4]. The obtained [Intermediate polyester 4] had a mass average molecular weight of 29,000, a glass transition temperature (Tg) of 31 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 15.7 mgKOH / g.
Next, 250 parts of the [intermediate polyester 4], 16.1 parts of isophorone diisocyanate, and 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. By reacting for a time, [Prepolymer 4] was synthesized. The isocyanate mass% of the obtained [Prepolymer 4] was 1.14% .

(Comparative Example 1)
-Production of Toner 6-
In Example 1, instead of [Prepolymer 1], [Prepolymer 5] synthesized as follows was used, except that 1.3 parts of isophoronediamine was changed to 3.2 parts. Thus, [Toner 6] was produced.

-Synthesis of Prepolymer 5-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 parts and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 to 15 mmHg to synthesize [Intermediate Polyester 5]. The resulting [intermediate polyester 5] has a number average molecular weight = 2,100, a weight average molecular weight = 9,500, a glass transition temperature (Tg) = 55 ° C., an acid value = 0.5 mgKOH / g, and a hydroxyl value = 51 mgKOH. / G.
Next, 410 parts of [intermediate polyester 5], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 5] was synthesized. The obtained [Prepolymer 5] had a free isocyanate mass% of 2.95% .

(Comparative Example 2)
-Production of Toner 7-
In Example 2, instead of [Prepolymer 1], [Prepolymer 5] synthesized as described above was used, except that 1.2 parts of isophoronediamine was changed to 3.2 parts. Thus, [Toner 7] was produced.

Next, about each polyester resin in Examples 1-5 and Comparative Examples 1-2, and the polyester resin precursor, the solubility with respect to ethyl acetate and the solubility parameter (Sp value) were evaluated as follows. The results are shown in Table 1.
The obtained toners of Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated for heat resistant storage stability, fixability, and charging characteristics as follows. The results are shown in Table 2.

<Solubility in ethyl acetate>
When each polyester resin or polyester resin precursor is dissolved in 0.5% by mass in ethyl acetate, the visible light region having a transmittance of 99.5% or more is soluble in ethyl acetate, and the transmittance is 99.99%. The case of less than 5% was determined to be insoluble in ethyl acetate.

<Calculation of Sp value>
The solubility parameter (Sp) value of each polyester resin or polyester resin precursor is determined by the method of Fedors using the additivity of atomic groups [Poly. Eng. Sci. , 14 (2) 147 (1974)].
Specifically, the low molecular polyester 1 of Example 1 is decomposed into atomic groups such as —CH ₂ —, —CH ₃ , —COO—, and a phenyl group, and the Sp value is calculated by conforming to the Fedors method. did.
The prepolymer 1 of Example 1 is decomposed into atomic groups such as —CH ₂ —, —CH ₃ , —COO—, phenyl group, —NCO—, and COONH—, and has an Sp value by conforming to the method of Fedors. Calculated.
The ethyl acetate insoluble polyester resin 1 of Example 1 was decomposed into atomic groups such as —CH ₂ —, —CH ₃ , —COO—, phenyl group, —NHCO—, and the Sp value was determined by conforming to the Fedors method. Calculated.
For other examples and comparative examples, Sp values were calculated in the same manner as in Example 1.

<Heat resistant storage stability>
Each toner was stored at 50 ° C. for 8 hours, and then screened with a 42 mesh screen for 2 minutes. In addition, the residual ratio is smaller as the toner has better heat-resistant storage stability.
〔Evaluation criteria〕
×: 30% or more △: 20% or more, less than 30% ○: 10% or more, less than 20% ◎: Less than 10%

<Fixability>
Using an image forming apparatus (Ricoh Co., Ltd., Imagio Neo 450), a plain image (Ricoh Co., Ltd., type 6200) and a cardboard recording medium (NBS Ricoh Co., Ltd., copy printing paper <135>) with a solid image , 1.0 ± 0.1 mg / cm ² of toner is adjusted so as to be developed, and the temperature of the fixing belt is adjusted to be variable, so that the temperature at which hot offset does not occur on plain paper The lower limit fixing temperature was measured. The minimum fixing temperature was determined as the fixing minimum temperature at which the remaining ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

<Charging characteristics>
(1) Stirring for 15 seconds Q / M
100 parts of a silicone resin-coated ferrite carrier (average particle size = 50 μm) and 4 parts of each toner were placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, and determined by a blow-off method.
(2) 10 minutes stirring Q / M
In the same manner as (1) above, the amount of charge when stirring for 10 minutes was determined.

<Comprehensive evaluation>
The above evaluation results were comprehensively judged and evaluated according to the following criteria.
○: Good ×: Bad

  The toner of the present invention can achieve both excellent low-temperature fixability and anti-offset performance, and is suitably used for high-quality electrophotographic image formation. The developer, toner-containing container, process cartridge, image forming apparatus, and image forming method of the present invention using the toner of the present invention are suitably used for high-quality electrophotographic image formation.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic configuration diagram showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 3 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 4 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 5 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 6 is a schematic configuration diagram showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 7 is a schematic enlarged view of the image forming element portion of FIG.

Explanation of symbols

1 Electrostatic latent image carrier (photosensitive drum)
DESCRIPTION OF SYMBOLS 2 Transfer apparatus 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feeding apparatus 7 Fixing apparatus 8 Cleaning apparatus 9 Intermediate transfer body cleaning apparatus 10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure apparatus 22 Secondary transfer apparatus 23 Roller 24 Secondary transfer belt 25 Fixing apparatus 26 Fixing belt 27 Pressure roller 28 Sheet reversing apparatus 30 Exposure apparatus 32 Contact glass 33 1st traveling body 34 2nd Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 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 Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 switching claw 56 discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 cleaning device 64 discharge device 70 discharge lamp 80 transfer roller 90 cleaning device 95 recording medium 100 image forming device 101 electrostatic latent image Carrier 102 Charging device 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developing device 130 Document table 142 Paper feed roller 143 Paper bank 1 44 Paper Feed Cassette 145 Separation Roller 146 Paper Feed Path 147 Transport Roller 148 Paper Feed Path 150 Copier Main Body 160 Charging Device 200 Paper Feed Table 210 Image Fixing Device 220 Heating Roller 230 Pressure Roller 300 Scanner 400 Automatic Document Feeder (ADF)

Claims (8)

Preparation at least active hydrogen group-containing compound, the active hydrogen group-containing compound and the polymer reactive, a toner material containing soluble non-modified polyester resin in ethyl acetate is dissolved or dispersed in an organic solvent a toner solution After that, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. A toner obtained by reacting to form an adhesive substrate in the form of particles,
The polymer capable of reacting with the active hydrogen group-containing compound includes at least an isocyanate group-containing polyester prepolymer, and the isocyanate group content based on JIS K1603 in the isocyanate group-containing polyester prepolymer is 2.0% by mass or less, the reaction product of an active hydrogen group-containing compound and the isocyanate group-containing polyester prepolymer is a polyester resin ethyl acetate-insoluble, the solubility parameter of the ethyl acetate-insoluble polyester resin as a SP1H, soluble non-denaturing to the ethyl acetate A toner satisfying the following formula: 0.3 ≦ (Sp1H−Sp1L) ≦ 1.0, where Sp1L is a solubility parameter of the polyester resin.   2. The toner according to claim 1, wherein a polymer that can react with an active hydrogen group-containing compound has a solubility parameter of Sp3, and satisfies the following formula: 0.3 ≦ (Sp3−Sp1L) ≦ 1.0.   The toner according to claim 1, wherein the isocyanate group-containing polyester prepolymer is soluble in ethyl acetate.   The toner according to claim 1, wherein the ethyl acetate insoluble polyester resin has a crosslinking point in the molecular chain.   The toner according to claim 1, wherein the ethyl acetate insoluble polyester resin contains a gel component.   The diol component in the isocyanate group-containing polyester prepolymer is at least one selected from 1,4-butanediol, propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol and 1,6-hexanediol. The toner according to any one of the above.   The toner according to claim 1, wherein the volume average particle diameter (Dv) is 3 μm to 8 μm, and the volume average particle diameter (Dv) / number average particle diameter (Dn) is 1.25 or less.   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 any one of claims 1 to 7 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.