JP2018066926A - Toner, developer, toner storage unit, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that prevents filming and has excellent low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage property.SOLUTION: A toner contains at least a crystalline polyester resin, amorphous polyester resin, and dispersed resin. The dispersed resin is a resin including a styrene-acrylic part and a polyester part. When the SP (solubility parameter) value (cal/cm) of the crystalline polyester resin is SP(1), the SP value of the amorphous polyester resin is SP(2), the SP value of the styrene-acrylic part of the dispersed resin is SP(A), and the SP value of the polyester part of the dispersed resin is SP(B), the relationships in the following formula (1) and formula (2) are satisfied. (1) |SP(1)-SP(A)|≤0.5; and (2) 0≤SP(2)-SP(B)≤0.5.SELECTED DRAWING: None

Description

  The present invention relates to a toner, a developer, a toner storage unit, an image forming apparatus, and an image forming method.

  In recent years, toners have been able to withstand high temperature and high humidity during storage and transportation after production, as well as reduction in particle size for high quality output images, high temperature offset resistance, low temperature fixability for energy saving. High heat-resistant storage stability is required. In particular, since power consumption during fixing accounts for much of the power consumption in the image forming process, it is very important to improve low-temperature fixability.

  Conventionally, toner prepared by a kneading and pulverizing method has been used. The toner produced by the kneading and pulverization method is difficult to reduce the particle size, the shape is irregular and the particle size distribution is broad, so the quality of the output image is not sufficient, and the fixing energy is high. There were problems such as. In addition, when a wax (release agent) is added to improve the fixability, the toner produced by the kneading and pulverization method cracks at the interface of the wax during pulverization, so that a large amount of wax exists on the toner surface. Resulting in. For this reason, there is a problem in that, while the releasing effect is produced, the toner (filming) is likely to adhere to the carrier, the photoreceptor and the blade, and the overall performance is not satisfactory.

  Therefore, in order to overcome the above-mentioned problems caused by the kneading and pulverizing method, a toner manufacturing method by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than that of the toner produced by the pulverization method, and the release agent can be included. . As a method for producing a toner by a polymerization method, for the purpose of improving low-temperature fixability and improving high-temperature offset resistance, a method of producing a toner from an extension reaction product of urethane-modified polyester as a toner binder is disclosed. (For example, refer to Patent Document 1).

  Also disclosed is a method for producing a toner that is excellent in powder flowability and transferability in the case of a small particle size toner, and also excellent in all of heat-resistant storage stability, low-temperature fixability, and high-temperature offset resistance (for example, Patent Documents 2 and 3). Further, a method for producing a toner having an aging step for producing a toner binder having a stable molecular weight distribution and achieving both low-temperature fixability and high-temperature offset resistance is disclosed (for example, see Patent Documents 4 and 5). .

In order to obtain a high level of low-temperature fixability, a toner containing a resin containing a crystalline polyester resin and a release agent and having a sea-island-like phase separation structure in which the resin and the wax are incompatible with each other has been proposed. (For example, refer to Patent Document 6).
Further, a toner containing a crystalline polyester resin, a release agent, and a graft polymer has been proposed (see, for example, Patent Document 7).

  Therefore, a toner containing a graft-modified polymer has been proposed for the purpose of obtaining a high level of low-temperature fixability, heat-resistant storage stability, and high-temperature offset resistance without filming. (For example, see Patent Document 8)

However, it is sufficiently satisfactory from the viewpoint of a toner having a high level required in recent years, that is, a toner having no filming and having excellent low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage stability. There was room for research because the toner was not obtained.
An object of the present invention is to provide a toner having no filming and having excellent low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage stability.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner comprising at least a crystalline polyester resin, an amorphous polyester resin, and a dispersion resin, wherein the dispersion resin is a resin having a styrene acrylic part and a polyester part, The SP (solubility parameter) value (cal ^1/2 / cm ^3/2 ) of the crystalline polyester resin is SP (1), the SP value of the amorphous polyester resin is SP (2), and the styrene acrylic part of the dispersion resin. When the SP value of the dispersion resin is SP (A) and the SP value of the polyester portion of the dispersion resin is SP (B), the relationship of the following formulas (1) to (2) is satisfied.
| SP (1) -SP (A) | ≦ 0.5 (1)
0 ≦ SP (2) −SP (B) ≦ 0.5 (2)

  According to the present invention, it is possible to provide a toner having no filming and having excellent low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage stability.

FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention.

(toner)
The toner of the present invention contains at least a crystalline polyester resin, an amorphous polyester resin, and a dispersion resin, and further contains other components as necessary.
The dispersion resin is a resin having a styrene acrylic part and a polyester part.
As a result of examination of the prior art by the present inventors, it has been found that the toners described in Patent Documents 4 and 5 do not satisfy the high level of low-temperature fixability required in recent years. In addition, although the toners described in Patent Documents 6 to 8 have heat-resistant storage stability, high-temperature offset resistance, and low-temperature fixability, the dispersibility of the polyester resin and the release agent is not sufficient, thereby preventing uneven surface distribution. Therefore, there is a problem that filming occurs. It has been found that the toners described in Patent Documents 6 to 8 do not sufficiently satisfy the high level of heat storage stability and stress resistance required in recent years.
Accordingly, the present inventors have further studied in order to obtain a toner that does not have filming and that satisfies the high level of low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage stability that are required in recent years. As a result, it was found that a toner satisfying the following relationship is effective.

The SP (solubility parameter) value (cal ^1/2 / cm ^3/2 ) of the crystalline polyester resin is SP (1), the SP value of the amorphous polyester resin is SP (2), and the styrene acrylic of the dispersion resin. When the SP value of the part is SP (A) and the SP value of the polyester part of the dispersion resin is SP (B), the relationship of the following formulas (1) to (2) is satisfied.
| SP (1) -SP (A) | ≦ 0.5 (1)
0 ≦ SP (2) −SP (B) ≦ 0.5 (2)
Moreover, when SP value of the said dispersion resin is set to SP (3), the relationship of following formula (3) to formula (5) is satisfy | filled.
9.7 ≦ SP (1), SP (A) ≦ 10.4 (3)
10.7 ≦ SP (2), SP (B) ≦ 11.5 (4)
10.4 ≦ SP (3) ≦ 10.7 (5)

By satisfying the relationship of the above formulas (1) to (2), the dispersibility of the crystalline polyester resin in the toner can be improved.
Furthermore, by satisfying the relations of the above formulas (3) to (5), the crystalline polyester resin can be finely dispersed inside the toner more uniformly.
Therefore, the toner satisfying the above formulas (1) to (2), particularly preferably the above formulas (1) to (5) prevents filming of the crystalline polyester resin, and prevents high temperature offset resistance and resistance. Stress properties and heat-resistant storage stability can be improved and low-temperature fixability can be satisfied.

In the case of [| SP (1) -SP (A) |> 0.5], the dispersion effect of the dispersion resin with respect to the crystalline polyester resin is reduced, the dispersion diameter of the crystalline polyester resin is increased, and the toner surface The crystalline polyester resin tends to be unevenly distributed, and filming and contamination of the crystalline polyester resin are likely to occur.
In the case of [SP (2) -SP (B)> 0.5], the dispersion effect of the dispersion resin with respect to the crystalline polyester resin is reduced, the dispersion diameter of the crystalline polyester resin is increased, and The crystalline polyester resin tends to be unevenly distributed, and filming and contamination of the crystalline polyester resin are likely to occur.
In the case of [0> SP (2) -SP (B)], the dispersion effect of the dispersion resin with respect to the crystalline polyester resin is reduced, the dispersion diameter of the crystalline polyester resin is increased, and the crystallinity on the toner surface is increased. The polyester resin tends to be unevenly distributed, and filming and contamination of the crystalline polyester resin are likely to occur.

Furthermore, if [9.7 ≦ SP (1)], problems that may occur in the case of [9.7> SP (1)] described below can be effectively prevented. If [9.7> SP (1)], the difference in SP value between the crystalline polyester resin and the amorphous resin is increased, and the crystalline polyester resin in the toner is affected by the polar interaction. The toner is unevenly distributed in the vicinity of the toner surface, and there is a risk that the low-temperature fixing property, heat-resistant storage property, and stress resistance may deteriorate.
In particular, when stress is applied to the toner, the crystalline polyester resin unevenly distributed on the surface causes the toner to aggregate and the carrier is buried in the toner. If the toner aggregates or the carrier is buried in the toner, the stress resistance test result (charge amount) deteriorates. When the surface uneven distribution amount of the crystalline polyester resin is increased, the stress resistance may be deteriorated.

  If [10.7 ≧ SP (3)], a problem that may occur in the case of [10.7 <SP (3)] described below can be effectively prevented. In the case of [10.7 <SP (3)], the SP value difference between the crystalline polyester resin and the amorphous resin becomes large, and the crystalline polyester resin in the toner is near the toner surface due to the interaction of polarity. May be unevenly distributed, resulting in deterioration of low-temperature fixability, heat-resistant storage stability, and stress resistance.

  If [10.4 ≧ SP (1)], a problem that may occur in the case of [10.4 <SP (1)] described below can be effectively prevented. In the case of [10.4 <SP (1)], the compatibility between the crystalline polyester resin and the amorphous polyester resin is increased, and the crystalline polyester resin in the toner is dispersed inside the toner. There is a possibility that the crystallinity of the heat-resistant polyester resin is lowered and the heat-resistant storage stability is deteriorated.

  If [10.4 ≦ SP (3)], problems that may occur in the case of [10.4> SP (3)] described below can be effectively prevented. In the case of [10.4> SP (3)], the compatibility between the crystalline polyester resin and the amorphous polyester resin is increased, and the crystalline polyester resin in the toner is dispersed inside the toner. There is a possibility that the crystallinity of the heat-resistant polyester resin is lowered and the heat-resistant storage stability is deteriorated.

<Amorphous polyester resin>
The amorphous polyester resin is obtained using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
In the present invention, as described above, the amorphous polyester resin uses a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. Those obtained by modifying a polyester resin, for example, a prepolymer described later, and a resin obtained by crosslinking and / or elongation reaction of the prepolymer do not belong to the amorphous polyester resin.

  Examples of the polyhydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxy). Alkylene) (2 to 3 carbon atoms) oxide (average number of added moles 1 to 10) adduct of bisphenol A such as phenyl) propane; ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated Bisphenol A, sorbitol, or their alkylene (C2-C3) oxide (average addition mole number 1-10) adduct etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyvalent carboxylic acid component include dicarboxylic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octyl succinic acid; Examples thereof include succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms; trimellitic acid, pyromellitic acid; anhydrides of these acids and alkyl (C1 to C8) esters of these acids. These may be used individually by 1 type and may use 2 or more types together.

  It is preferable that at least a part of the amorphous polyester resin is compatible with a prepolymer described later and a resin obtained by crosslinking and / or elongation reaction of the prepolymer. When these are compatible, low-temperature fixability and high-temperature offset resistance can be improved. For this reason, the polyhydric alcohol component and polyvalent carboxylic acid component constituting the amorphous polyester resin and the polyhydric alcohol component and polycarboxylic acid component constituting the prepolymer described below may have similar compositions. preferable.

The molecular weight of the amorphous polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. In some cases, the durability is inferior, and when the molecular weight is too high, the viscoelasticity at the time of melting of the toner becomes high and the low-temperature fixability may be inferior. It is preferable that they are 1,000, 4,000, number average molecular weight (Mn) 1,000-4,000, and Mw / Mn 1.0-4.0.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 3,000-6,000, number average molecular weight (Mn) 1,500-3,000, and Mw / Mn 1.0-3.5.

  There is no restriction | limiting in particular as an acid value of the said amorphous polyester resin, Although it can select suitably according to the objective, 1 mgKOH / g-50 mgKOH / g are preferable, and 5 mgKOH / g-30 mgKOH / g are more preferable. When the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved when fixing to paper, and the low-temperature fixability can be improved. . When the acid value is 50 mgKOH / g or less, charging stability, particularly charging stability against environmental fluctuations, does not decrease.

  There is no restriction | limiting in particular as a hydroxyl value of the said amorphous polyester resin, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

  The glass transition temperature (Tg) of the amorphous polyester resin is not particularly limited and can be appropriately selected according to the purpose. However, if the Tg is too low, the heat resistant storage stability of the toner, The durability against stress such as stirring may be inferior, and if the Tg is too high, the viscoelasticity at the time of melting of the toner may be high and the low-temperature fixability may be inferior. -60 degreeC is more preferable.

  There is no restriction | limiting in particular as content of the said amorphous polyester resin, Although it can select suitably according to the objective, 50 mass parts-95 mass parts are preferable with respect to 100 mass parts of the said toner, and 60 masses. Part to 90 parts by mass is more preferable. When the content is 50 parts by mass or more, it is possible to effectively prevent the problem that the dispersibility of the pigment and the release agent in the toner is deteriorated and the image is likely to be fogged or disturbed. When the amount is 95 parts by mass or less, the problem that the low-temperature fixability is inferior due to the decrease in the content of the crystalline polyester can be effectively prevented. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality, high stability, and low temperature fixability.

The molecular structure of the amorphous polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

<Crystalline polyester resin>
The crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic diol.
The saturated aliphatic diol is preferably a linear aliphatic diol having 2 to 8 carbon atoms. As a result, the crystalline polyester resin can be uniformly finely dispersed inside the toner, preventing filming of the crystalline polyester resin, improving stress resistance, and achieving low-temperature fixability of the toner. be able to.

  Since the crystalline polyester resin has high crystallinity, it exhibits a heat-melting characteristic that exhibits a sudden viscosity drop near the fixing start temperature. By using the crystalline polyester resin having such characteristics for the toner, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and the viscosity is rapidly lowered (sharp melt property) at the melting start temperature and fixing. As a result, a toner having both good heat storage stability and low-temperature fixability can be obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).

The crystalline polyester resin is obtained using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
In the present invention, the crystalline polyester resin, as described above, uses a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. The crystalline polyester resin that is obtained by modifying the crystalline polyester resin, for example, a prepolymer described later and a resin obtained by crosslinking and / or elongation reaction of the prepolymer does not belong to the crystalline polyester resin.

<< polyhydric alcohol component >>
There is no restriction | limiting in particular as said polyhydric alcohol component, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and straight chain having 2 to 8 carbon atoms. A chain saturated aliphatic diol is more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin may be lowered, and the melting point may be lowered. Further, if the main chain portion has 2 or more carbon atoms, it is possible to effectively prevent the problem that, when polycondensation with an aromatic dicarboxylic acid, the melting temperature becomes high and low-temperature fixing may become difficult. it can. On the other hand, if the number of carbon atoms is 8 or less, it is practically easy to obtain the material.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 in that the crystalline polyester resin has high crystallinity and excellent sharp melt properties. -Hexanediol is preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

<< Polyvalent carboxylic acid component >>
As the polyvalent carboxylic acid component, sebacic acid is used, but other divalent carboxylic acids and trivalent or higher carboxylic acids can be used in combination depending on the purpose.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower alkyl esters thereof.

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. And the lower alkyl esters.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid component may include a dicarboxylic acid component having a sulfonic acid group. Further, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained.
These may be used individually by 1 type and may use 2 or more types together.

  In addition, when maleic acid, succinic acid, fumaric acid, terefluic acid, and derivatives thereof are used as the component of the crystalline polyester resin, although the crystalline polyester resin is obtained, the SP value of the obtained crystalline polyester resin Is generally high, and it is difficult to satisfy the relations of the expressions (1) and (3) in the toner.

There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin fat, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. If the melting point is 60 ° C. or higher, it is possible to effectively prevent the problem that the crystalline polyester resin is easily melted at a low temperature and the heat resistant storage stability of the toner may be lowered. When the temperature is less than 80 ° C., it is possible to effectively prevent a problem that the polyester resin is not sufficiently melted by heating at the time of fixing and the low-temperature fixability may be lowered.
The melting point can be measured by an endothermic peak value of a DSC chart in a differential scanning calorimeter (DSC) measurement.

The molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and many components have a low molecular weight. From the viewpoint that heat-resistant storage stability deteriorates, the soluble content of orthodichlorobenzene in the crystalline polyester resin is determined by GPC measurement to have a weight average molecular weight (Mw) of 3,000 to 30,000 and a number average molecular weight (Mn). It is preferably 1,000 to 10,000 and Mw / Mn 1.0 to 10.
Furthermore, it is preferable that they are weight average molecular weight (Mw) 5,000-15,000, number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.

  The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.

  The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and good charging characteristics, 0 mgKOH / G to 50 mgKOH / g are preferable, and 5 mgKOH / g to 50 mgKOH / g are more preferable.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As a simple example, there is a method of detecting, as a crystalline polyester resin, an infrared absorption spectrum having an absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ .

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 2 mass parts-20 mass parts are preferable with respect to 100 mass parts of said toners, 5 mass parts -15 mass parts is more preferable. When the content is 2 parts by mass or more, it is possible to effectively prevent the problem that the low-temperature fixability is inferior because sharp melting with the crystalline polyester resin is insufficient. If it is 20 mass parts or less, the problem that heat-resistant storage stability deteriorates and it becomes easy to produce the fog of an image can be prevented effectively. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality, high stability, and low-temperature fixability.

The particle size of the crystalline polyester resin is preferably 0.1 μm to 2.0 μm. When the particle diameter of the crystalline polyester resin is increased, the exposure of the crystalline polyester resin to the toner surface increases, and filming may be deteriorated.
The particle diameter of the crystalline polyester resin can be measured by observing a toner cross section with a scanning electron microscope (SEM) or the like.

<Dispersed resin>
The dispersion resin is a resin having a styrene acrylic part and a polyester part. Here, the styrene acrylic part means a styrene acrylic resin component having a structural unit derived from a raw material monomer of a styrene acrylic resin, and the polyester part is a polyester having a structural unit derived from a raw material monomer of a polyester resin. This refers to a resin component.
The dispersion resin is a composite resin formed by partially chemically bonding a polyester resin component (polyester resin unit) and a styrene acrylic resin component (styrene acrylic resin unit).
When the dispersion resin has a polyester resin unit, the dispersibility of the crystalline polyester resin in the toner can be improved. This enables the crystalline polyester resin to be uniformly finely dispersed in the toner, preventing filming of the crystalline polyester resin and the release agent, improving stress resistance, and toner. Low temperature fixability can be achieved.
The styrene acrylic resin unit contained in the dispersion resin includes a styrene resin component and an acrylic resin component, thereby increasing the affinity with the amorphous polyester resin and improving the dispersion effect on the crystalline polyester resin. The crystalline polyester resin is easily finely dispersed inside the toner.

  As a dispersion resin, in addition to a mixture of raw material monomers of two polymerization resins of a polyester resin unit and a styrene acrylic resin unit, it also reacts with any of the raw material monomers of the two polymerization resins as one of the raw material monomers. A resin obtained by mixing monomers capable of being mixed (both reactive monomers) is preferred.

  Both reactive monomers have at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, an ethylenically unsaturated bond, It is preferable to use a monomer having such a property, and by using such a bireactive monomer, it is possible to improve the dispersibility of the resin to be a dispersed phase. Specific examples of the both reactive monomers include acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid and the like. Among these, acrylic acid, methacrylic acid and fumaric acid are preferable.

  As for the usage-amount of both a reactive monomer, 0.1-10 mass parts is preferable with respect to 100 mass parts of raw material monomers of a polyester-type resin. In the present invention, the bi-reactive monomer is treated as a monomer different from the raw material monomer for the polyester-based resin and the raw material monomer for the addition-polymerized resin because of the specificity of the performance.

  In the present invention, when the dispersion resin is obtained by performing the two polymerization reactions using the above raw material monomer mixture and the both reactive monomers, the progress and completion of the polymerization reaction are simultaneous in time. It is not necessary to select the reaction temperature and time appropriately according to each reaction mechanism, and to proceed and complete the reaction.

  For example, in the method for producing a dispersion resin in the present invention, a raw material monomer for a polyester resin, a raw material monomer for an addition polymerization resin, a catalyst such as a bireactive monomer, a polymerization initiator, etc. are mixed. To obtain an addition polymerization resin component having a functional group capable of polycondensation reaction by radical polymerization reaction, and then raise the reaction temperature to 190 to 270 ° C., and then the polyester resin component is mainly formed by condensation polymerization reaction. Preferably.

  The softening point of the dispersion resin is desirably 80 to 170 ° C, preferably 90 to 160 ° C, and more preferably 95 to 155 ° C.

  The mass ratio of the crystalline polyester resin and the dispersion resin is not particularly limited, but the ratio of the crystalline polyester resin: the dispersion resin is preferably 50/100 to 200/100.

As the raw material monomer of the polyester resin constituting the dispersion resin, the same raw material monomer as that of the crystalline polyester resin can be used, but it is preferable that a succinic acid derivative is used as the carboxylic acid component.
Styrene derivatives such as styrene, α-methylstyrene, vinyltoluene and the like are used as raw material monomers for the styrene acrylic resin constituting the dispersion resin.
The content of the styrene derivative is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more in the raw material monomer of the styrene acrylic resin.

  Examples of raw material monomers for styrene acrylic resins that can be used in addition to styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N- Examples thereof include N-vinyl compounds such as vinyl pyrrolidone.

  Of these, (meth) acrylic acid alkyl esters are preferred from the viewpoint of low-temperature fixability and charge stability of the toner. From the above viewpoint, the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 22, and more preferably 8 to 18. In addition, carbon number of this alkyl ester says carbon number derived from the alcohol component which comprises ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like.

  The content of the (meth) acrylic acid alkyl ester is preferably 50% by mass or less, more preferably 30% by mass or less, in the raw material monomer of the styrene acrylic resin, from the viewpoints of low-temperature fixability, storage stability and charge stability of the toner. Preferably, 20 mass% or less is more preferable.

The styrene acrylic part of the dispersion resin has a styrene unit part having a structure represented by the following structural formula (1a) and a (meth) acryl unit part having a structure represented by the following structural formula (1b). It is preferable.


In particular, n in the structural formula (1b) is 4 to 10, and R is preferably a hydrogen atom or a methyl group.
If [4 ≦ n] in the structural formula (1), problems that may occur in the case of [4> n] described below can be effectively prevented. In the case of [4> n], the dispersion effect of the dispersion resin on the crystalline polyester resin is reduced, the dispersion diameter of the crystalline polyester resin is increased, and the crystalline polyester resin is likely to be unevenly distributed on the toner surface. Filming and contamination of the crystalline polyester resin are likely to occur.
If [10 ≧ n] in the structural formula (1), problems that may occur in the case of [10 <n] described below can be effectively prevented. In the case of [10 <n], the dispersion effect of the dispersion resin on the crystalline polyester resin is reduced, the dispersion diameter of the crystalline polyester resin is increased, and the crystalline polyester resin is likely to be unevenly distributed on the toner surface. Filming and contamination of the crystalline polyester resin are likely to occur.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a release agent, a colorant, a polymer having a site capable of reacting with an active hydrogen group-containing compound, an active hydrogen group Examples of the compound include a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material.

<< Releasing agent >>
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things.
Examples of release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; And natural waxes such as petroleum waxes such as paraffin, microcrystalline, and petrolatum.

In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, and chlorinated hydrocarbons; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

  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, 60 degreeC or more and less than 95 degreeC are preferable.

More preferably, a hydrocarbon wax having a melting point of 60 ° C. or higher and lower than 95 ° C. is used as the release agent. Since such a release agent can effectively act as a release agent between the fixing roller and the toner interface, high temperature offset resistance can be achieved without applying a release agent such as oil to the fixing roller. Can be improved.
In particular, the hydrocarbon wax has almost no compatibility with the crystalline polyester resin and can function independently of each other. Therefore, the softening effect of the crystalline polyester resin as a binder resin, the offset of the release agent. It is preferable because it does not impair the performance.
When the melting point of the release agent is 60 ° C. or higher, it is possible to effectively prevent the problem that the release agent is easily melted at a low temperature and the heat resistant storage stability of the toner is poor. When the melting point of the release agent is less than 95 ° C., it is possible to effectively prevent the problem that the release agent is not sufficiently melted by heating at the time of fixing and sufficient offset property cannot be obtained.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 8 parts by mass is more preferable. When the content is 2 parts by mass or more, it is possible to effectively prevent the problem that the high temperature offset resistance during fixing and the low temperature fixing property are poor. If it is 10 mass parts or less, the problem that heat-resistant storage stability deteriorates and it becomes easy to produce the fog of an image etc. can be prevented effectively. When the content is in the more preferable range, it is advantageous in terms of improving the image quality and improving the fixing stability.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, 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 Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor 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, Resol Rubin GX Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Examples include green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and ritbon.
There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded with the production of the masterbatch or the masterbatch include, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, or a substituted polymer thereof in addition to the dispersion resin; styrene-p-chlorostyrene Copolymer, Styrene-propylene copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, 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 Copolymerization, styrene-acrylonitrile copolymerization , Styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer of polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, Examples thereof include modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and may use 2 or more types together.

  The masterbatch can be obtained by mixing a masterbatch resin and a colorant under high shear force and kneading to obtain a masterbatch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<< Polymer having a site capable of reacting with active hydrogen group-containing compound (prepolymer) >>
The polymer having a site capable of reacting with the active hydrogen group-containing compound (sometimes referred to as “prepolymer”) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyol resin, Examples thereof include polyacrylic resins, polyester resins, epoxy resins, and derivatives thereof. These may be used individually by 1 type and may use 2 or more types together.
Among these, a polyester resin is preferable in terms of high fluidity and transparency at the time of melting.

Examples of the site capable of reacting with the active hydrogen group-containing compound of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by -COCl. These may be used individually by 1 type and may use 2 or more types together.
Among these, an isocyanate group is preferable.

  There is no restriction | limiting in particular as said prepolymer, According to the objective, it can select suitably. However, it is easy to adjust the molecular weight of the polymer component, and it is possible to ensure good releasability and fixability even when there is no oil-less low-temperature fixing property in dry toners, particularly when there is no release oil application mechanism to the heating medium for fixing. In this respect, a polyester resin having an isocyanate group or the like capable of generating a urea bond is preferable.

<<< Polyester resin containing isocyanate group >>>
The polyester resin containing an isocyanate group (hereinafter sometimes referred to as “polyester prepolymer having an isocyanate group”) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a carboxylic acid and a polyisocyanate.

-Polyol-
There is no restriction | limiting in particular as said polyol, According to the objective, it can select suitably, For example, diol, trihydric or more alcohol, the mixture of diol and trihydric or more alcohol, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diol, and a mixture of diol and a small amount of trihydric or higher alcohol are preferable.

The diol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6 -Alkylene glycol such as hexanediol; diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc. Alicyclic diols; those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to alicyclic diols; bisphenol A, bisphenol F, bisphenol S Bisphenols; the bisphenols include ethylene oxide, propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide; and the like. In addition, there is no restriction | limiting in particular as carbon number of the said alkylene glycol, Although it can select suitably according to the objective, 2-12 are preferable.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. And a mixture thereof is more preferable.

The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, trihydric or higher aliphatic alcohol, trihydric or higher polyphenol, alkylene of trihydric or higher polyphenols. And oxide adducts.
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
The trihydric or higher polyphenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolac, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trihydric or higher polyphenols.
When the diol and the trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is not particularly limited and may be appropriately selected depending on the intended purpose. % To 10% by mass is preferable, and 0.01% to 1% by mass is more preferable.

-Polycarboxylic acid-
The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acids, trivalent or higher carboxylic acids, and mixtures of dicarboxylic acids and trivalent or higher carboxylic acids. It is done. These may be used individually by 1 type and may use 2 or more types together.
Among these, a dicarboxylic acid, a mixture of a dicarboxylic acid and a small amount of a tricarboxylic or higher polycarboxylic acid is preferable.

There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, bivalent alkanoic acid, bivalent alkenoic acid, aromatic dicarboxylic acid, etc. are mentioned.
The divalent alkanoic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid and sebacic acid.
There is no restriction | limiting in particular as said divalent alkenoic acid, Although it can select suitably according to the objective, C4-C20 bivalent alkenoic acid is preferable. There is no restriction | limiting in particular as said C4-C20 bivalent alkenoic acid, According to the objective, it can select suitably, For example, a maleic acid, a fumaric acid, etc. are mentioned.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, C8-C20 aromatic dicarboxylic acid is preferable. There is no restriction | limiting in particular as said C8-C20 aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.

The trivalent or higher carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trivalent or higher aromatic carboxylic acids.
There is no restriction | limiting in particular as said trivalent or more aromatic carboxylic acid, Although it can select suitably according to the objective, C9-C20 trivalent or more aromatic carboxylic acid is preferable. There is no restriction | limiting in particular as said C9-C20 trivalent or more aromatic carboxylic acid, According to the objective, it can select suitably, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

As the polycarboxylic acid, an acid anhydride or a lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid may be used.
There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester, etc. are mentioned.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are used in combination, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. 0.01 mass% to 10 mass% is preferable, and 0.01 mass% to 1 mass% is more preferable.

  The equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid in the polycondensation of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. ˜2 is preferable, 1 to 1.5 is more preferable, and 1.02 to 1.3 is particularly preferable.

There is no restriction | limiting in particular as content of the structural unit derived from the polyol in the polyester prepolymer which has the said isocyanate group, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable.
When the content is 0.5% by mass or more, it is possible to effectively prevent the problem that the high-temperature offset resistance is lowered and it is difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. If it is 40 mass% or less, the problem that low-temperature fixability falls can be prevented effectively.

-Polyisocyanate-
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and phenol derivatives thereof. , Oxime, caprolactam and the like blocked.

  The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

  The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

  The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.

The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is not particularly limited and may be appropriately selected depending on the purpose. 1-5 are preferable, 1.2-4 are more preferable, and 1.5-3 are especially preferable. If the equivalent ratio is 1 or more, the problem that the offset resistance is lowered can be effectively prevented. If it is 5 or less, the problem that the low-temperature fixability is lowered can be effectively prevented.

  There is no restriction | limiting in particular as content of the structural unit derived from polyisocyanate in the polyester prepolymer which has the said isocyanate group, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are preferable. 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable. When the content is 0.5% by mass or more, a decrease in high temperature offset resistance can be prevented, and when the content is 40% by mass or less, a decrease in low temperature fixability can be prevented.

  There is no restriction | limiting in particular as an average number of the isocyanate groups which the polyester prepolymer which has the said isocyanate group has per molecule, Although it can select suitably according to the objective, 1 or more are preferable and 1.2-5 are More preferably, 1.5-4 is especially preferable. When the average number is 1 or more, it is possible to effectively prevent the problem that the molecular weight of the urea-modified polyester resin is lowered and the high temperature offset resistance is lowered.

  The mass ratio of the polyester prepolymer having an isocyanate group to the polyester resin containing a propylene oxide adduct of bisphenol in the polyhydric alcohol component and having a specific hydroxyl value and an acid value is particularly limited. However, 5/95 to 25/75 is preferable, and 10/90 to 25/75 is more preferable. If the mass ratio is 5/95 or more, the high temperature offset resistance can be prevented from being lowered, and if it is 25/75 or less, the low temperature fixability and the gloss of the image can be prevented from being lowered.

<< Active hydrogen group-containing compound >>
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer having a site capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction or the like in an aqueous medium.

  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 and 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.

The active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. The polymer having a site capable of reacting with the active hydrogen group-containing compound is a polyester resin containing an isocyanate group. In some cases, amines are preferred because they can be polymerized with the polyester resin by elongation reaction, crosslinking reaction, or the like.
The amines are not particularly limited and can be appropriately selected according to the purpose. Examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those amino groups blocked. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of trivalent or higher amine are preferable.

  There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine, etc. are mentioned. There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane, etc. are mentioned. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. Can be mentioned. There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. are mentioned.

  The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples thereof include ketimine compounds and oxazolidone compounds.

<< Charge Control Agent >>
There is no restriction | limiting in particular as said charge control agent, According to the objective, it can select suitably. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Is mentioned.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the toner. 2 mass parts-5 mass parts are more preferable. If the content is 10 parts by mass or less, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, and the fluidity of the developer is reduced. In addition, it is possible to effectively prevent the problem of reducing the image density. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they may be added when dissolved and dispersed directly in an organic solvent, or fixed after preparation of toner particles on the toner surface. You may let them.

<< External additive >>
As the external additive, in addition to oxide fine particles, inorganic fine particles and hydrophobic treated inorganic fine particles can be used in combination. The average particle diameter of the hydrophobized inorganic fine particles is preferably 1 nm to 100 nm, more preferably 5 nm to 70 nm.
In addition, the hydrophobized inorganic fine particles preferably include at least one inorganic fine particle of 20 nm or less and at least one inorganic fine particle of 30 nm or more. In addition, the specific surface area by BET method ^is preferably 20m ² / g~500m 2 / g.

  There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.), metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like.

  Suitable external additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Moreover, as titania fine particles, for example, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all of which are manufactured by Teika Corporation), and the like.

  Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Industry Co., Ltd.), TAF-500T, and TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  In order to obtain hydrophobized oxide microparticles, hydrophobized silica microparticles, hydrophobized titania microparticles, and hydrophobized alumina microparticles, hydrophilic microparticles can be obtained using methyltrimethoxysilane or methyltrimethylsilane. It can be obtained by treating with a silane coupling agent such as ethoxysilane or octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.1 mass%-5 mass% are preferable with respect to the said toner, 0.3 mass%-3 The mass% is more preferable.
There is no restriction | limiting in particular as an average particle diameter of the primary particle of the said inorganic fine particle, Although it can select suitably according to the objective, 100 nm or less is preferable and 3 nm or more and 70 nm or less are more preferable. If the thickness is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exerted effectively. If the thickness is larger than this range, the surface of the photoreceptor may be damaged unevenly.

<< Flowability improver >>
The fluidity improver is not particularly limited and may be appropriately selected depending on the purpose as long as it can perform surface treatment to increase hydrophobicity and prevent deterioration of fluidity characteristics and charging characteristics even under high humidity. be able to. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like can be given. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

<< Cleaning improver >>
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photosensitive member or the primary transfer medium, and is appropriately selected according to the purpose. Can do. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

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

<Toner characteristics>
[Toner acid value]
The acid value of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of controlling low temperature fixability (fixing lower limit temperature), hot offset occurrence temperature, etc., 0.5 mgKOH / g It is preferably ˜40 mg KOH / g. If the acid value is 0.5 mgKOH / g or more, the effect of improving the dispersion stability by the base during production cannot be obtained, or the extension reaction and / or the cross-linking reaction proceeds when the prepolymer is used. It is possible to effectively prevent the problem that the manufacturing stability is lowered. When the acid value is 40 mgKOH / g or less, when the prepolymer is used, the extension reaction and / or the crosslinking reaction become insufficient, and the problem that the high temperature offset resistance is lowered can be effectively prevented. .

[Glass transition temperature (Tg) of toner]
The glass transition temperature (Tg) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. The glass transition temperature (Tg1st) calculated at the first temperature increase in DSC measurement is 45 ° C. It is preferable that it is above 65 degreeC, and it is more preferable that it is 50 degreeC or more and 60 degrees C or less. Thereby, low temperature fixability, heat resistant storage stability and high durability can be obtained. If Tg1st is 45 ° C. or higher, blocking in the developing machine and filming on the photoreceptor can be prevented, and if it is lower than 65 ° C., low temperature fixability can be prevented. .
The glass transition temperature (Tg2nd) calculated at the second temperature increase in the DSC measurement of the toner is preferably 20 ° C. or higher and lower than 40 ° C. If the Tg2nd is 20 ° C. or higher, blocking in the developing machine and filming on the photoreceptor can be prevented, and if it is lower than 40 ° C., the low-temperature fixability can be prevented from being lowered.

[Volume average particle diameter of toner]
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

<Calculation method and analysis method of various characteristics of toner and toner component>
<< SP value >>
The SP value (solubility parameter / Solubility Parameter) will be described.
The SP value is a so-called solubility parameter (also referred to as a solubility parameter or a solubility parameter), and is a numerical value indicating how easily each other is soluble. The SP value is expressed as a square root of an attractive force between molecules, that is, a cohesive energy density (CED). The CED is the amount of energy required to evaporate 1 mL.

The calculation of the SP value (cal ^1/2 / cm ^3/2 ) in the present invention can be performed using the following formula (I) by the Fedors method.
SP value (dissolution parameter) = (CED value) ^1/2 = (E / V) ^1/2 ··· Formula (I)
In the above formula (I), E is the molecular aggregation energy (cal / mol), V is the molecular volume (cm ³ / mol), the evaporation energy of the atomic group is Δei, and the molar volume is Δvi, respectively, (II), represented by formula (III).
E = ΣΔei Formula (II)
V = ΣΔvi Formula (III)

Although there are various theories on the calculation method of the SP value, the method of Fedors generally used in the present invention is used.
The data described in “Basic Theory of Adhesion” (Akira Imoto, published by Kobunshi Shuppankai, Chapter 5) are used for this calculation method and various data of evaporation energy Δei and molar volume Δvi of each atomic group.
For those not shown such as -CF ₃ group, R.I. F. Fedors, Polym. Eng. Sci. 14, 147 (1974).
For reference, when the SP value represented by the formula (I) is converted to (J / cm ³ ) ^1/2 , 2.046 is converted to SI unit (J / m ³ ) ^1/2 . In that case, it may be multiplied by 2,046.
For example, when each of the amorphous polyester resin, the crystalline polyester resin, and the dispersion resin is synthesized and mixed, the SP value can be easily calculated as described above.

Usually, it is difficult to calculate the SP value from the charged composition ratio in a resin in which a monomer is added during the polymerization to change the resin skeleton. In addition, the composition of the components contained in the toner is generally unknown, and it is difficult to calculate the SP value.
However, the calculation of the SP value by the Fedors method can be performed by specifying the type and ratio of the monomer constituting the resin or the like.
For example, the mixture of the amorphous polyester resin, the crystalline polyester resin, the dispersion resin, etc. is separated by GPC, and the SP value of the SP value is obtained by taking the analysis method described below for each separated component. Calculation is possible.

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

  The SP value calculated by the Fedors method can be calculated by specifying the type and ratio of the monomer constituting the resin, but the SP value in the present invention is the ratio when the monomer type is specified by the above analysis. The respective composition ratios were added in order from the highest, and the composition was calculated from the monomer composition when the total reached 90 mol% of the total (that is, the SP value was calculated for the remaining monomers). We decided not to add).

<< Component Analysis of Toner >>
An analysis means for analyzing the toner and calculating the SP value is shown.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .
The monomer composition and composition ratio of the amorphous polyester resin, the crystalline polyester resin, and the dispersion resin contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens)
7.1 ppm to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
Around 6.8 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens) and from double bond of fumaric acid (for 2 hydrogens)
5.2 ppm to around 5.4 ppm: methine derived from bisphenol A propylene oxide adduct (one hydrogen)
3.7 ppm to around 4.7 ppm: bisphenol A propylene oxide adduct derived from methylene (for 2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (for 4 hydrogens)
Around 1.6 ppm: It can be derived from the methyl group of bisphenol A (for 6 hydrogen atoms).
From these results, the SP value of the crystalline polyester resin and the dispersion resin can be calculated by the formula (I).

<< Method for Measuring Acid Value and Hydroxyl Value >>
The hydroxyl value can be measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1 to 2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are as follows.

〔Measurement condition〕
Still
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
Measurement 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
Steppes 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
Potential1 No
Potentialial No
Stop for revaluation No

The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g in the case of an ethyl acetate-soluble component) is added to 120 mL of toluene and dissolved by stirring at 23 ° C. for about 10 hours. Next, 30 mL of ethanol is added to prepare a sample solution. When the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran is used. Furthermore, an acid value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 mL of toluene and 30 mL of ethanol is used.
At this time, the measurement conditions are the same as in the case of the hydroxyl value described above.

  The acid value can be measured as described above. Specifically, titration is performed with a 0.1N potassium hydroxide / alcohol solution standardized in advance, and the acid value [mg KOH / g] = The acid value is calculated by titration [mL] × N × 56.1 [mg / mL] / sample mass [g] (where N is a factor of 0.1 N potassium hydroxide / alcohol solution).

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from 0 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. Thereafter, the temperature is lowered from 150 ° C. to 0 ° C. at a temperature drop rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rise rate of 10 ° C./min, and a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation) ) To measure the DSC curve.
From the obtained DSC curve, using the analysis program “endothermic shoulder temperature” in the DSC-60 system, the DSC curve at the first temperature rise is selected, and the glass transition temperature at the first temperature rise of the target sample is obtained. Can do. Further, by using the “endothermic shoulder temperature”, a DSC curve at the second temperature rise can be selected, and the glass transition temperature at the second temperature rise of the target sample can be obtained.
Also, from the obtained DSC curve, using the analysis program “endothermic peak temperature” in the DSC-60 system, the DSC curve at the first temperature increase is selected, and the melting point at the first temperature increase of the target sample is obtained. Can do. Further, by using the “endothermic peak temperature”, a DSC curve at the second temperature rise can be selected, and the melting point at the second temperature rise of the target sample can be obtained.

In the present invention, the glass transition temperature at the first temperature rise when the toner is used as the target sample is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
Moreover, in this invention, melting | fusing point and Tg at the time of the 2nd temperature rise of each structural component are made into melting | fusing point and Tg of each object sample.

<< Measurement Method of Particle Size Distribution >>
For the volume average particle diameter (D4) and number average particle diameter (Dn) of the toner, the ratio (D4 / Dn) is, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter Co., Ltd.) or the like. Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) as a dispersant is added to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic aqueous solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<Toner production method>
The toner production method is not particularly limited and may be appropriately selected depending on the intended purpose. However, the toner includes at least the amorphous polyester resin, the crystalline polyester resin, the release agent, and the dispersion. It is preferable to granulate by dispersing an oil phase containing a resin and the colorant in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method.
Further, as another example of the method for producing the toner, the toner is produced by an elongation reaction and / or a cross-linking reaction between the active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound (hereinafter referred to as “the toner”). A method for forming toner base particles while producing an “adhesive substrate”) is shown below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, removal of an organic solvent, and the like are performed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. There is no restriction | limiting in particular in the addition amount in the aqueous medium of the said resin particle, Although it can select suitably according to the objective, 0.5 mass%-10 mass% are preferable. There is no restriction | limiting in particular as said resin particle, 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, surfactant is preferable.

There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol, etc. are mentioned. The lower ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include acetone and methyl ethyl ketone.

-Preparation of oil phase-
The oil phase containing the toner material is prepared by preparing the active hydrogen group-containing compound, the polymer having a site capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin, and the amorphous material in an organic solvent. The toner material containing a polyester resin, the release agent, the dispersion resin, the colorant, and the like can be dissolved or dispersed.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when the toner material is emulsified or dispersed, the adhesive base material is obtained by subjecting the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group-containing compound to an extension reaction and / or a crosslinking reaction. Generate.

  The adhesive base material is an aqueous medium containing an oil phase containing a polymer having reactivity to active hydrogen groups such as a polyester prepolymer having an isocyanate group, together with a compound containing active hydrogen groups such as amines. It may be produced by emulsifying or dispersing in an aqueous medium and subjecting both to an extension reaction and / or a crosslinking reaction in an aqueous medium. Alternatively, the oil phase containing the toner material may be produced by emulsifying or dispersing in an aqueous medium to which a compound having an active hydrogen group has been added in advance, and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. Good. Alternatively, after emulsifying or dispersing the oil phase containing the toner material in an aqueous medium, a compound having an active hydrogen group is added, and both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface in the aqueous medium. May be generated. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the adhesive substrate are not particularly limited, and an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, Depending on the combination, it can be selected as appropriate.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 40 to 98 degreeC is more preferable.

  There is no particular limitation on the method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in the aqueous medium. For example, there may be mentioned a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase and dispersed by shearing force.

The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.
There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 degreeC-150 degreeC is preferable under pressure, and 40 degreeC-98 degreeC is more preferable. In general, dispersion is easier when the dispersion temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. It is 50 to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is 50 parts by mass or more, it is possible to effectively prevent the problem that the toner material is not dispersed and the toner base particles having a predetermined particle diameter cannot be obtained. If it is 2,000 parts by mass or less, the production cost can be reduced.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly 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.

The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, etc. Can be used.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester, etc. are mentioned.
Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the cross-linking reaction in producing the adhesive substrate.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, dibutyltin laurate, dioctyltin laurate, etc. are mentioned.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples thereof include a method of evaporating the organic solvent, a method of spraying the dispersion liquid in a dry atmosphere, and removing the organic solvent in the oil droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, And a method of causing the particles to collide with each other or a suitable collision plate.
The apparatus used in the above method is not particularly limited and may be appropriately selected depending on the purpose. Apparatus, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), an automatic mortar, and the like.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.
When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, and members such as a filming of the toner on the developing roller and a blade for thinning the toner The toner is less fused to the toner, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.
When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 90% by mass to 98% by mass, and 93% by mass to 97% by mass. More preferred.

<Career>
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 a core material is preferable.

−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50 emu / g-90 emu / g manganese-strontium type material, manganese-magnesium type material, etc. are mentioned. . In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable.
When the volume average particle diameter is 10 μm or more, the problem that the fine powder increases in the carrier, the magnetization per particle is lowered, and the carrier is scattered can be effectively prevented. If the thickness is 150 μm or less, the specific surface area may be reduced, toner scattering may occur, and in the case of a full color with many solid portions, particularly the problem that the reproduction of the solid portions may be effectively prevented. .

-Resin layer-
The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, Examples include fluoroterpolymers such as copolymers of tetrafluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said amino-type resin, According to the objective, it can select suitably, For example, a urea-formaldehyde resin, a melamine resin, a benzoguanamine resin, a urea resin, a polyamide resin, an epoxy resin etc. are mentioned.
There is no restriction | limiting in particular as said polyvinyl-type resin, According to the objective, it can select suitably, For example, an acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. are mentioned. .
There is no restriction | limiting in particular as said polystyrene resin, According to the objective, it can select suitably, For example, a polystyrene, a styrene-acryl copolymer, etc. are mentioned.
The polyhalogenated olefin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyvinyl chloride.
There is no restriction | limiting in particular as said polyester-type resin, According to the objective, it can select suitably, For example, a polyethylene terephthalate, a polybutylene terephthalate, etc. are mentioned.

  The resin layer may contain conductive powder or the like as necessary. There is no restriction | limiting in particular as said electrically conductive powder, According to the objective, it can select suitably, For example, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide, etc. are mentioned. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do.
There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, a dip coating method, a spray method, a brush coating method etc. can be used.
There is no restriction | limiting in particular as said solvent, According to the objective, it can select suitably, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve, etc. are mentioned.
The baking may be an external heating method or an internal heating method. For example, a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method used, etc. are mentioned.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is 0.01% by mass or more, the problem that a uniform resin layer cannot be formed on the surface of the core material can be effectively prevented. If it is 5.0 mass% or less, since the resin layer is thick, fusion between carriers occurs, and the problem that the uniformity of the carrier is lowered can be effectively prevented.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least an electrostatic latent image carrier (also referred to as an image carrier) and a developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit.
By mounting the toner containing unit of the present invention on an image forming apparatus to form an image, there is no filming, and the toner having excellent low-temperature fixability, high-temperature offset resistance, stress resistance, and heat-resistant storage stability is obtained. It is possible to perform image formation utilizing the characteristics.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.
More preferably, the image forming apparatus of the present invention is an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image carrier. The electrostatic latent image formed on the body is developed with toner to form a toner image, and a developing means including toner, and the toner image formed on the electrostatic latent image carrier are transferred to a recording medium Transfer means for transferring to the surface, and fixing means for fixing the toner image transferred to the surface of the recording medium.
In the image forming method of the present invention, more preferably, an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier and the electrostatic latent image carrier formed on the electrostatic latent image carrier. A developing process for developing the electrostatic latent image with toner to form a toner image, a transfer process for transferring the toner image formed on the electrostatic latent image carrier onto the surface of the recording medium, and the recording A fixing step of fixing the toner image transferred onto the surface of the medium.
The toner is used in the developing unit and the developing step. Preferably, the toner image may be formed by using a developer containing the toner and further containing other components such as a carrier as necessary.

  Next, one aspect of the image forming apparatus of the present invention will be described with reference to FIG. A color image forming apparatus 100A shown in FIG. 1 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the An exposure apparatus 30 as an exposure means, a developing device 40 as the development means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

  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. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. Also, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) a developed image (toner image) onto a transfer sheet 95 as a recording medium. The intermediate transfer member 50 is disposed opposite to the intermediate transfer member 50. 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 arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

The developing device 40 includes a developing belt 41 as the developer carrier, a black (Bk) developing unit 45K, a yellow (Y) developing unit 45Y, a magenta (M) developing unit 45M, And a cyan (C) developing unit 45C. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. 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.
Hereinafter, specific modes of the image forming method will be described.
Image data sent to an image processing unit (hereinafter referred to as “IPU”) creates image signals of four colors of Y (yellow), M (magenta), C (cyan), and K (black).
Next, each image signal of Y, M, C, and K is transmitted to the writing unit in the image processing unit. The writing section modulates and scans four laser beams for Y, M, C, and K, respectively, and after charging the photosensitive drum by the charging section, an electrostatic latent image is sequentially formed on each photosensitive drum. . Here, for example, the first photosensitive drum corresponds to K, the second photosensitive drum corresponds to Y, the third photosensitive drum corresponds to M, and the fourth photosensitive drum corresponds to C.
Next, a toner image of each color is formed on the photosensitive drum by a developing unit as a developing attachment unit. Further, the transfer paper fed by the paper feed unit is conveyed on the transfer belt, and the toner images on the photosensitive drum are sequentially transferred onto the transfer paper by the transfer charger.
After the transfer process, the transfer paper is conveyed to a fixing unit, and the transferred toner image is fixed on the transfer paper by the fixing unit.
After the transfer process is completed, the toner remaining on the photosensitive drum is removed by the cleaning unit.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “%” Represents “% by mass”, and “part” represents “part by mass” unless otherwise specified.

(Production Example 1-1)
<Synthesis of Crystalline Polyester Resin 1>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, 2,120 g of sebacic acid, 0.021 g of 1,9-nonanedicarboxylic acid, 1.200 g of 1,6-hexanediol, Put. After reacting at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester resin 1.
The crystalline polyester resin 1 had an SP value of 9.85 and a melting point of 68.5 ° C. GPC measurement of the soluble content of orthodichlorobenzene in the crystalline polyester resin 1 revealed that Mw was 30,000, Mn was 6,900, and Mw / Mn was 4.4.

(Production Example 1-2)
<Synthesis of crystalline polyester resin 2>
A 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple was charged with 2,120 g of sebacic acid, 0.021 g of 1,9-nonanedicarboxylic acid, 1.200 g of 1,2-ethanediol, Put. After reacting at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester resin 2.
The crystalline polyester resin 2 had an SP value of 10.20 and a melting point of 69.0 ° C. When the soluble content of orthodichlorobenzene in the crystalline polyester resin 2 was measured by GPC, Mw was 15,000, Mn was 4,900, and Mw / Mn was 3.1.

(Production Example 1-3)
<Synthesis of crystalline polyester resin 3>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 2,020 g of 1,10-decanedicarboxylic acid, 1,000 g of 1,8-octanediol, 1,4-butanediol 1,420 g and hydroquinone 3.9 g were added. After reacting at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester resin 3.
The crystalline polyester resin 3 had an SP value of 9.60 and a melting point of 68.0 ° C. GPC measurement of the soluble content of orthodichlorobenzene in the crystalline polyester resin 3 revealed that Mw was 15,000, Mn was 4,900, and Mw / Mn was 3.1.

(Production Example 1-4)
<Synthesis of Crystalline Polyester Resin 4>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,120 g of 1,10-decanedicarboxylic acid, 1,900 g of 1,10-decanediol, and 3.9 g of hydroquinone I put it in. After reacting at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystalline polyester resin 4.
The crystalline polyester resin 4 had an SP value of 9.70 and a melting point of 71.0 ° C. GPC measurement of the soluble content of orthodichlorobenzene in crystalline polyester resin 4 revealed that Mw was 16,000, Mn was 5,000, and Mw / Mn was 3.2.

The characteristic values of the crystalline polyester resins 1 to 4 are summarized in Table 1.

(Production Example 2-1)
<Synthesis of Amorphous Polyester Resin 1>
Into a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 499 parts of bisphenol A ethylene oxide side 2 mol adduct, 229 parts of bisphenol A propylene oxide 3 mol adduct, 100 parts isophthalic acid 108 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added. After reacting at 230 ° C. for 10 hours at normal pressure and further 5 hours at a reduced pressure of 10 mmHg to 15 mmHg, 30 parts of trimellitic anhydride is placed in the reaction vessel, and reacted at 180 ° C. and normal pressure for 3 hours to produce amorphous. Quality polyester resin 1 was obtained.
The SP value of the amorphous polyester resin 1 was 11.30.
Amorphous polyester resin 1 had a weight average molecular weight of 5,500, a number average molecular weight of 1,800, a Tg of 50 ° C., and an acid value of 20 mgKOH / g.

(Production Example 2-2)
<Synthesis of Amorphous Polyester Resin 2>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 229 parts of bisphenol A ethylene oxide side 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, 70 parts isophthalic acid 98 parts of terephthalic acid, 46 parts of fumaric acid, 24 parts of dodecenyl succinic acid and 2 parts of dibutyltin oxide were added. After introducing nitrogen gas into the container and keeping the temperature in an inert atmosphere and raising the temperature, a copolycondensation reaction was performed at 230 ° C. for 12 hours, and then the pressure was gradually reduced at 230 ° C. to obtain an amorphous polyester resin 2. .
The SP value of the amorphous polyester resin 2 was 10.82.
Amorphous polyester resin 2 had a weight average molecular weight of 17,400, a number average molecular weight of 6,700, a Tg of 61 ° C., and an acid value of 14 mgKOH / g.

The characteristic values of the amorphous polyester resin are summarized in Table 2.

(Production Example 3-1)
<Synthesis of Dispersing Resin 1>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 7.2 g of 2,3-butanediol, 6.08 g of 1,2-propanediol, 18.59 g of terephthalic acid, 2 -0.18 g of tin (II) ethylhexanoate was added. Nitrogen gas is introduced into the container and heated in an inert atmosphere, heated at 180 ° C. for 1 hour, then heated from 180 ° C. to 230 ° C. at 10 ° C./hr, and then condensed at 230 ° C. for 10 hours. The reaction was further carried out at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 160 ° C., 1.0 g of lauryl acrylate, 8.50 g of styrene, 1.48 g of 2-ethylhexyl acrylate, and dibutyl peroxide were added dropwise over 1 hour using a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and the temperature was raised to 210 ° C. Then, 4.61 g of trimellitic anhydride was added, and the reaction was performed at 210 ° C. for 2 hours. Reaction was carried out at 210 ° C. and 10 kPa until a desired softening point was reached, to obtain dispersion resin 1.
The SP value of dispersion resin 1 was 10.31, the SP value of the styrene acrylic part of dispersion resin 1 was 9.83, and the SP value of the polyester part of dispersion resin 1 was 10.76.
Dispersion resin 1 had a weight average molecular weight of 79,000, a number average molecular weight of 2,800, and a Tg of 49.5 ° C.

(Production Example 3-2)
<Synthesis of Dispersing Resin 2>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 7.2 g of 2,3-butanediol, 6.08 g of 1,2-propanediol, 18.59 g of terephthalic acid, 2 -0.18 g of tin (II) ethylhexanoate was added. Nitrogen gas is introduced into the container and heated in an inert atmosphere, heated at 180 ° C. for 1 hour, then heated from 180 ° C. to 230 ° C. at 10 ° C./hr, and then condensed at 230 ° C. for 10 hours. The reaction was further carried out at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 160 ° C., 1.0 g of octyl acrylate, 8.50 g of styrene, 1.48 g of 2-ethylhexyl acrylate, and dibutyl peroxide were added dropwise over 1 hour using a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and the temperature was raised to 210 ° C. Then, 4.61 g of trimellitic anhydride was added, and the reaction was performed at 210 ° C. for 2 hours. Reaction was carried out at 210 ° C. and 10 kPa until a desired softening point was reached, to obtain dispersion resin 2.
The SP value of dispersion resin 2 was 10.60, the SP value of the styrene acrylic part of dispersion resin 2 was 10.34, and the SP value of the polyester part of dispersion resin 2 was 10.73.
Dispersion resin 2 had a weight average molecular weight of 26,000, a number average molecular weight of 3,400, and a Tg of 61.6 ° C.

(Production Example 3-3)
<Synthesis of Dispersing Resin 3>
To a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 7.2 g of 2,3-butanediol, 6.08 g of 1,2-propanediol, 18.59 g of terephthalic acid, 2 -0.18 g of tin (II) ethylhexanoate was added. Nitrogen gas is introduced into the container and heated in an inert atmosphere, heated at 180 ° C. for 1 hour, then heated from 180 ° C. to 230 ° C. at 10 ° C./hr, and then condensed at 230 ° C. for 10 hours. The reaction was further carried out at 230 ° C. and 8.0 kPa for 1 hour. After cooling to 160 ° C., 1.0 g of butyl acrylate, 8.50 g of styrene, 1.48 g of 2-ethylhexyl acrylate, and dibutyl peroxide were added dropwise over 1 hour using a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and the temperature was raised to 210 ° C. Then, 4.61 g of trimellitic anhydride was added, and the reaction was performed at 210 ° C. for 2 hours. The reaction was carried out at 210 ° C. and 10 kPa until a desired softening point was reached, whereby Dispersing Resin 3 was obtained.
The SP value of the dispersion resin 3 was 10.63, the SP value of the styrene acrylic part of the dispersion resin 3 was 10.11, and the SP value of the polyester part of the dispersion resin 3 was 10.82.
The dispersion resin 3 had a weight average molecular weight of 120,000, a number average molecular weight of 3,000, and a Tg of 58.5 ° C.

The characteristic values of the dispersion resin are summarized in Table 3.

(Production Example 4-1)
<Preparation of crystalline polyester resin dispersion 1>
100 parts of crystalline polyester resin 1 and 200 parts of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice water bath at a rate of 27 ° C./min. To this, 500 mL of glass beads (3 mmφ) was added, and pulverized for 10 hours with a batch type sand mill (manufactured by Campehapio Co., Ltd.) to obtain a crystalline polyester resin dispersion 1.

(Production Example 4-2)
<Preparation of crystalline polyester resin dispersion 2>
A crystalline polyester resin dispersion 2 was obtained in the same manner as in Production Example 4-1, except that the crystalline polyester resin 1 was replaced with the crystalline polyester resin 2 in Production Example 4-1.

(Production Example 4-3)
<Preparation of crystalline polyester resin dispersion 3>
A crystalline polyester resin dispersion 3 was obtained in the same manner as in Production Example 4-1, except that the crystalline polyester resin 1 was replaced with the crystalline polyester resin 3 in Production Example 4-1.

(Production Example 4-4)
<Preparation of crystalline polyester resin dispersion 4>
A crystalline polyester resin dispersion 4 was obtained in the same manner as in Production Example 4-1, except that the crystalline polyester resin 1 was replaced with the crystalline polyester resin 4 in Production Example 4-1.

Example 1
<Preparation of Toner 1>
-Preparation of oil phase-
--Synthesis of prepolymer--
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 Part and 2 parts of dibutyltin oxide. The reaction was carried out at 230 ° C. for 8 hours at normal pressure, and further for 5 hours under reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester 1].
[Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Prepolymer 1] was obtained.
[Prepolymer 1] had a free isocyanate mass% of 1.53%.

--Synthesis of ketimine--
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1].
The amine value of [ketimine compound 1] was 418 mgKOH / g.

--Synthesis of master batch (MB)-
1,200 parts of water, carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] 540 parts, and 1,200 parts of amorphous polyester resin 2 were added, and Henschel mixer (Mitsui (Mine company). The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

--- Preparation of pigment / WAX dispersion-
In a container in which a stir bar and a thermometer are set, 378 parts of [Amorphous polyester resin 1] and 50 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75.0) C, SP value 8.8), 22 parts of CCA (salicylic acid metal complex E-84: manufactured by Orient Chemical Co., Ltd.), and 947 parts of ethyl acetate were charged. The temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1,324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80. Dispersion was performed under the conditions of volume% filling and 3 passes. Next, 1,042.3 parts of a 65% ethyl acetate solution of [Amorphous Polyester Resin 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1].
The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

  [Pigment / WAX dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Crystalline polyester resin dispersion 1] 73.9 parts, [Dispersion resin 3] 73.9 parts, and [Ketimine compound 1] 4.6 parts was put into a container and mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute to obtain [Oil Phase 1].

-Synthesis of organic fine particle emulsion (fine particle dispersion)-
In a reaction vessel equipped with a stirrer 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), 138 parts of styrene, 138 parts of methacrylic acid , And 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of an aqueous 1% ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours. Dispersion 1] was obtained.
The volume average particle size of the [fine particle dispersion 1] measured with LA-920 (manufactured by HORIBA) was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

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

-Emulsification / solvent removal-
1,200 parts of [Aqueous Phase 1] was added to the container containing [Oil Phase 1], and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

-Cleaning and drying-
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution 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: 12,000 rpm for 10 minutes), and then filtered.
(4): The operation of (1) to (5) above, wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. Was performed twice to obtain [Filter cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

  Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin.

<Evaluation>
A developer was prepared for the obtained toner by the following method, and the following evaluation was performed. The results are shown in Table 8.
<< Preparation of developer >>
-Production of carrier-
To 100 parts of toluene, 100 parts of a silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black were added. A resin layer coating solution was prepared by dispersing with a homomixer for 20 minutes. Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.
-Production of developer-
Using a ball mill, 5 parts of the toner 1 and 95 parts of the carrier were mixed to prepare a developer.

<< Low-temperature fixability and high-temperature offset resistance >>
A copying test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus in which a fixing unit of a copying machine MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) and the high temperature offset temperature (fixing upper limit temperature) were determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm / second to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / second, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.

<< Heat resistant storage stability >>
A 50 mL glass container was filled with 10 g of toner and sufficiently tapped until there was no change in the apparent density of the toner powder. The container was covered and allowed to stand in a thermostatic bath at 50 ° C. for 24 hours, then cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991). The heat resistant storage stability was evaluated according to the following criteria. In addition, the greater the penetration, the better the heat-resistant storage stability, and those having a penetration of less than 15 mm are more likely to cause problems in use.
〔Evaluation criteria〕
◎: Needle penetration is 25 mm or more ○: Needle penetration is 20 mm or more and less than 25 mm △: Needle penetration is 15 mm or more and less than 20 mm ×: Needle penetration is less than 15 mm

<< Filming >>
The image forming apparatus MF2800 (manufactured by Ricoh Co., Ltd.) was used to visually inspect the photoconductor after 10,000 images were formed, and the toner component, mainly the release agent, was fixed to the photoconductor. It was evaluated according to the following evaluation criteria.
A: The toner component is not fixed to the photoconductor. A: The toner component is fixed to the photoconductor. However, this is not a practical problem. Δ: The toner component is fixed to the photoconductor. , Is a level that causes a problem in practical use ×: The toner component can be firmly fixed to the photoconductor, and is a level having a large problem in practical use.

<< Stress resistance >>
0.25 g of toner and 4.75 g of carrier were placed in a stainless steel container having a bottom diameter of 25 mm and a height of 30 mm. A rotation of 300 rpm was applied in the circumferential direction for 20 minutes, and the toner and the carrier were stirred and brought into contact with each other. Here, ferrite particles (manufactured by Ricoh Co., Ltd.) having an average particle diameter of 35 μm were used as the carrier.
The charge amount (Q / S) per unit area of the agitated toner was measured by a blow-off method using a charge amount measuring device TB-200 (manufactured by Toshiba Corporation).
Specifically, a measurement sample is loaded into a sample part equipped with a 400 mesh stainless steel screen of the above charge amount measuring apparatus, and a blow pressure of 50 kPa (0.5 kgf) in a normal temperature and humidity environment (20 ° C., 55% RH). / Cm ² ) nitrogen gas was blown for 10 seconds to measure the charge.
〔Evaluation criteria〕
◎: less than the absolute value of charging amount 220μC / ^{m 2} or more 260μC / ^{m 2} ○: the absolute value of charging amount 170C / ^{m 2} or more 220μC / ^m less than ² △: the absolute value of charging amount 120μC / ^{m 2} or more 170μC / m ² less ×: overall evaluation by the charge amount of the absolute value is less than 50 .mu.C / m ² or more 120MyuC / m ² this evaluation, when stressed to the toner cohesion degree of toner particles, the retracted state of the carrier can do.

(Example 2)
<Preparation of toner>
A toner was obtained in the same manner as in Example 1 except that [Amorphous polyester resin 1] was replaced with [Amorphous polyester resin 2] in Example 1. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Example 3)
<Preparation of toner>
A toner was obtained in the same manner as in Example 2, except that [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 2]. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

Example 4
<Preparation of toner>
A toner was obtained in the same manner as in Example 2 except that [Dispersion Resin 3] was replaced with [Dispersion Resin 1] in Example 2. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Example 5)
<Preparation of toner>
A toner was obtained in the same manner as in Example 4 except that [Dispersion Resin 1] was changed to [Dispersion Resin 2] in Example 4. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Example 6)
<Preparation of toner>
A toner was obtained in the same manner as in Example 5, except that [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 2]. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 1)
<Preparation of toner>
In Example 1, [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 3], and [Dispersion resin 3] was replaced with [Dispersion resin 1]. A toner was obtained. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 2)
<Preparation of toner>
A toner was obtained in the same manner as in Comparative Example 1 except that [Dispersion Resin 1] was replaced with [Dispersion Resin 3] in Comparative Example 1. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 3)
<Preparation of toner>
In Comparative Example 2, a toner was prepared in the same manner as in Comparative Example 2 except that [Amorphous polyester resin 1] was replaced with [Amorphous polyester resin 2] and [Dispersion resin 3] was replaced with [Dispersion resin 2]. Got. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 4)
<Preparation of toner>
A toner was obtained in the same manner as in Comparative Example 1 except that [Crystalline Polyester Resin Dispersion 3] was replaced with [Crystalline Polyester Resin Dispersion 1] in Comparative Example 1. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 5)
<Preparation of toner>
Comparative Example 1 was the same as Comparative Example 1 except that [Crystalline Polyester Resin Dispersion 3] was replaced with [Crystalline Polyester Resin Dispersion 2] and [Dispersion Resin 1] was replaced with [Dispersion Resin 2]. A toner was obtained. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

(Comparative Example 6)
<Preparation of toner>
A toner was obtained in the same manner as in Comparative Example 3, except that [Crystalline Polyester Resin Dispersion 3] was replaced with [Crystalline Polyester Resin Dispersion 4] in Comparative Example 3. Tables 4 to 7 below show the SP value of each component in the obtained toner, the relationship between the SP values, and the relationship at n in the structural formula (1b) of the dispersion resin. The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 8.

As described above, in Examples 1 to 6, toners excellent in all of low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, stress resistance, and filming were obtained. In addition, by adjusting the SP value of the crystalline polyester resin, amorphous polyester resin, dispersion resin, styrene acrylic part of the dispersion resin, and polyester part of the dispersion resin, heat resistant storage stability, stress resistance, and filming were improved. A toner was obtained.
In Comparative Example 1, the formula (2) is not satisfied, and further, the n number in the formula (3), the formula (5), and the structural formula (1) is not satisfied. It is presumed that the dispersion effect of the crystalline polyester resin on the crystalline polyester resin is not sufficient, and the heat resistant storage stability and stress resistance are greatly deteriorated.
In Comparative Example 2, the formula (1) is not satisfied and the formula (3) is not satisfied, and the dispersion effect of the amorphous polyester resin on the crystalline polyester resin is not sufficient due to the polar interaction. It is presumed that the heat-resistant storage stability and stress resistance deteriorated.
In Comparative Example 3, the formula (1) is not satisfied, the formula (3) is not satisfied, and the dispersion effect of the amorphous polyester resin on the crystalline polyester resin is not sufficient due to the polar interaction. It is presumed that the crystalline polyester resin is unevenly distributed on the toner surface and the heat resistant storage stability is greatly deteriorated.
In Comparative Example 4, the formula (2) is not satisfied, and the n number in the formula (5) and the structural formula (1) is not satisfied. It is presumed that the dispersion effect on the heat-resistant polyester resin is not sufficient, and the heat resistant storage stability and stress resistance are greatly deteriorated.
In Comparative Example 5, the formula (2) was not satisfied, and due to the polar interaction, the dispersion effect of the amorphous polyester resin with respect to the crystalline polyester resin was not sufficient, and the heat resistant storage stability and the stress resistance deteriorated. It is guessed.
In Comparative Example 6, Formula (1) is not satisfied, and due to the polar interaction, the dispersion effect of the amorphous polyester resin on the crystalline polyester resin is not sufficient, and the crystalline polyester resin is unevenly distributed on the toner surface. It is presumed that filming has greatly deteriorated.

Aspects of the present invention are as follows, for example.
<1> A toner comprising at least a crystalline polyester resin, an amorphous polyester resin, and a dispersion resin,
The dispersion resin is a resin having a styrene acrylic part and a polyester part,
The SP (solubility parameter) value (cal ^1/2 / cm ^3/2 ) of the crystalline polyester resin is SP (1), the SP value of the amorphous polyester resin is SP (2), and the styrene acrylic of the dispersion resin. The toner satisfies the relationship of the following formulas (1) to (2) where the SP value of the part is SP (A) and the SP value of the polyester part of the dispersion resin is SP (B). .
| SP (1) -SP (A) | ≦ 0.5 (1)
0 ≦ SP (2) −SP (B) ≦ 0.5 (2)
<2> The toner according to <1>, wherein the dispersion resin satisfies the relationship of the following formulas (3) to (5) when the SP value of the dispersion resin is SP (3).
9.7 ≦ SP (1), SP (A) ≦ 10.4 (3)
10.7 ≦ SP (2), SP (B) ≦ 11.5 (4)
10.4 ≦ SP (3) ≦ 10.7 (5)
<3> The toner according to any one of <1> to <2>, wherein the crystalline polyester resin has a structural unit derived from a linear aliphatic diol having 2 to 8 carbon atoms.
<4> The dispersion resin is
It has a structure represented by the following structural formula (1a) and a structure represented by the following structural formula (1b),
The toner according to any one of <1> to <3>, wherein n in the structural formula (1b) is 4 to 10, and R is a hydrogen atom or a methyl group.

<5> A developer comprising the toner according to any one of <1> to <4>.
<6> A toner storage unit that stores the toner according to any one of <1> to <4>.
<7> an electrostatic latent image carrier, and electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
Transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <4>.
<8> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
A transfer step of transferring a toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing the toner image transferred to the surface of the recording medium,
The toner is the toner according to any one of <1> to <4>, wherein the toner is an image forming method.

  <1> to <4>, the toner according to <5>, the developer according to <5>, the toner storage unit according to <6>, the image forming apparatus according to <7>, the < According to the image forming method described in 8>, the above-described problems can be solved and the object of the present invention can be achieved.

DESCRIPTION OF SYMBOLS 10 Electrostatic latent image carrier 20 Charging means 30 Exposure means 40 Development means 50 Intermediate transfer body 60 Cleaning means 70 Static elimination means

Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent No. 2579150 JP 2001-158819 A JP 2004-46095 A JP 2007-271789 A JP 2012-53196 A

Claims (8)

A toner comprising at least a crystalline polyester resin, an amorphous polyester resin, and a dispersion resin,
The dispersion resin is a resin having a styrene acrylic part and a polyester part,
The SP (solubility parameter) value (cal ^1/2 / cm ^3/2 ) of the crystalline polyester resin is SP (1), the SP value of the amorphous polyester resin is SP (2), and the styrene acrylic of the dispersion resin. The toner satisfying the relationship of the following formulas (1) to (2), where SP (A) is the SP value of the part and SP (B) is the SP value of the polyester part of the dispersion resin.
| SP (1) -SP (A) | ≦ 0.5 (1)
0 ≦ SP (2) −SP (B) ≦ 0.5 (2) The toner according to claim 1, wherein when the SP value of the dispersion resin is SP (3), the toner satisfies the relationship of the following formulas (3) to (5).
9.7 ≦ SP (1), SP (A) ≦ 10.4 (3)
10.7 ≦ SP (2), SP (B) ≦ 11.5 (4)
10.4 ≦ SP (3) ≦ 10.7 (5)   The toner according to claim 1, wherein the crystalline polyester resin has a structural unit derived from a linear aliphatic diol having 2 to 8 carbon atoms. The dispersion resin is
It has a structure represented by the following structural formula (1a) and a structure represented by the following structural formula (1b),
The toner according to claim 1, wherein n in the structural formula (1b) is 4 to 10, and R is a hydrogen atom or a methyl group.

  A developer comprising the toner according to claim 1.   A toner containing unit containing the toner according to claim 1. An electrostatic latent image carrier, and electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
Transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing means for fixing the toner image transferred to the surface of the recording medium,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
A transfer step of transferring a toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
Fixing the toner image transferred to the surface of the recording medium,
The image forming method according to claim 1, wherein the toner is the toner according to claim 1.