JP6647071B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

  In recent years, with the widespread use of electrophotographic full-color copiers, higher speed, higher image quality, energy saving, and the like are required. As a specific energy saving measure, a toner that can be fixed at a lower fixing temperature is required in order to reduce power consumption in the fixing process. In order to achieve high image quality, it is required to increase the transfer efficiency of the toner image on the electrostatic latent image carrier to the intermediate transfer member and the transfer efficiency of the toner image on the intermediate transfer member to paper.

In order to achieve low-temperature fixing, a toner using a crystalline polyester resin as a plasticizer for an amorphous polyester resin has been proposed (see Patent Document 1). By using the crystalline polyester resin, a certain effect was obtained on the low-temperature fixability.
However, since the amorphous polyester resin has a monomer composition in which the wax and the amorphous polyester resin are incompatible with each other, the compatibility between the amorphous polyester resin and the crystalline polyester resin is also low. . Therefore, the crystalline polyester resin is not compatible with the amorphous polyester resin and exists as a crystal domain, and there is a side surface in which the effect as a plasticizer cannot be fully utilized.

  Therefore, from the viewpoint of enhancing the compatibility between the amorphous polyester resin and the crystalline polyester resin, a toner that defines the relationship between the compatibility parameter SP of the amorphous polyester resin (hereinafter, SP) and the SP of the crystalline polyester resin. Has been proposed (see Patent Document 2). By bringing the SP values close to each other, a further effect on the low-temperature fixability was obtained.

  On the other hand, in order to improve transfer efficiency, a proposal has been made in which inorganic fine particles having a large particle diameter serving as a spacer are fixed to the surface of toner particles (see Patent Document 3). The inorganic fine particles act as spacers at the interface between the toner and the electrostatic latent image carrier and between the toner and the intermediate transfer body, so that the contact area of the toner with the latent image carrier and the intermediate transfer body is reduced. Since the adhesion can be reduced, the transfer efficiency can be increased.

JP 2004-046095 A JP 2012-053196 A JP 2013-47754 A

In the toner of Patent Document 2, since all the amorphous polyester resin is plasticized, hot offset occurs in a severe environment in which a small-sized recording material is passed and then a large-sized recording material is passed. In some cases.
When a toner to which inorganic fine particles having a large particle diameter are fixed using the crystalline polyester resin of Patent Document 3 is subjected to image output for a long period of time in a high-temperature and high-humidity environment, the temperature in the copying machine body increases. Then, the plasticized amorphous polyester resin portion becomes more soft. In some cases, the inorganic fine particles having a large particle size serving as the spacer are embedded in the toner, and the transfer efficiency is reduced in some cases.

Furthermore, in recent years, multimedia compatibility that can handle not only plain paper but also various media such as thick paper and thin paper has been required. As the thick paper, not only a thick paper having a flat surface but also a paper having a relatively low surface smoothness such as embossed paper or rough paper having irregularities on the front surface and both sides is used. Since a sufficient transfer pressure is not applied to such paper, a part of the toner image on the intermediate transfer body is not transferred, and an image quality defect called a white spot may occur. Therefore, there is a demand for a toner having a higher transfer efficiency.
An object of the present invention is to provide a toner that solves the above-mentioned problems. Specifically, it is an object of the present invention to provide a toner capable of satisfying high transferability even in long-term image output while achieving both low-temperature fixability and hot offset resistance.

As a result of intensive studies, the present inventors have found that it is possible to obtain a toner that satisfies high transferability even in long-term image output while achieving both low-temperature fixing property and hot offset resistance. Was found.
The toner according to the present invention is a toner having toner particles containing an amorphous resin, a colorant, and a crystalline resin,
The amorphous resin contains a resin A containing polyester as a main component, a resin B containing polyester as a main component, and a resin C containing polyester as a main component,
The crystalline resin is a resin containing polyester as a main component,
The resin A has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 130 ° C. or more and 150 ° C. or less,
When the compatibility parameter of the resin A obtained by the equation of Fedors was SP (A), the SP (A) is a 12.55 ≦ SP (A) ≦ 13.00 ,
The resin B has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 80 ° C or more and 95 ° C or less,
When the compatibility parameter of the resin B obtained by the formula of Fedors was SP (B), the SP (B) is a 11.80 ≦ SP (B) ≦ 12.40 ,
The resin C has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 100 ° C or more and 120 ° C or less,
When the compatibility parameter of the resin C obtained by the equation of Fedors was SP (C), the SP (C), characterized in that a 12.40 ≦ SP (C) ≦ 12.55 .

  By using the toner of the present invention, it is possible to provide a toner capable of satisfying both high-temperature fixing property and hot offset resistance and satisfying high transferability even in long-term image output.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure of the thermal sphering processing apparatus used for this invention.

The toner of the present invention is a toner having toner particles containing an amorphous resin, a colorant, and a crystalline resin,
The amorphous resin contains a resin A containing polyester as a main component, a resin B containing polyester as a main component, and a resin C containing polyester as a main component,
The crystalline resin is a resin containing polyester as a main component,
The resin A has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 130 ° C. or more and 150 ° C. or less,
Compatibility parameter SP (A) determined by the Fedors equation is 12.55 ≦ SP (A) ≦ 13.00,
The resin B has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 80 ° C or more and 95 ° C or less,
Compatibility parameter SP (B) determined by the Fedors equation is 11.80 ≦ SP (B) ≦ 12.40,
The resin C has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 100 ° C or more and 120 ° C or less,
The compatibility parameter SP (C) determined by the Fedors equation is 12.40 ≦ SP (C) ≦ 12.55.

As described above, by bringing the compatibility parameters of the amorphous resin and the crystalline resin closer to each other, the low-temperature fixing property is improved, but hot offset may occur due to plasticization of the amorphous resin. .
Therefore, the present inventors have proposed that in order to achieve both low-temperature fixability and hot offset resistance,
Amorphous resin that is compatible with crystalline resin and contributes to improving low-temperature fixability by plasticizing,
Amorphous resin that phase-separates with crystalline resin and contributes to improved hot offset resistance by not plasticizing,
Considering that two kinds of amorphous resins are necessary, an attempt was made to study.

However, when a toner was formed by using a non-crystalline resin having a low softening point close to the crystalline resin and an SP value and an amorphous resin having a high softening point far from the crystalline resin and the SP value, the toner was evaluated. In both cases, the hot offset resistance was impaired. In addition, in long-term image output, transferability was also reduced.
The inventors of the present invention have found that the two types of amorphous resins have very different SP values, resulting in poor mixing properties between the resins and the formation of a sea-island phase separation structure. Regarding the above, it was considered that the amorphous resin having a high softening point existing as a domain had an adverse effect. Further, regarding the hot offset resistance, it was considered that the amorphous resin having a low softening point existing as a domain had an adverse effect. Further, an amorphous resin having a low softening point and an amorphous resin having a high softening point plasticized by the action of the crystalline resin are independently present. From this, it is considered that the burying of the inorganic fine particles having a large particle diameter as the spacer inside the toner was selectively reduced in the portion of the plasticized amorphous resin having a low softening point.

Therefore, the present inventors have further studied and found that the mixing property of two kinds of amorphous resins having different SP values can be improved as described below, and reached the present invention.
That is, for two types of amorphous resins that are far apart from each other in the SP value for controlling the compatibility with the crystalline resin and the phase separation property, the third SP, which is the middle SP value of the two types of amorphous resin, is used. Is added.
When the toner of the present invention was evaluated, the crystalline resin positively acts on the non-crystalline resin having a low softening point, so that the low-temperature fixability is further improved and the characteristics of the amorphous resin having a high softening point are further improved. Can be maintained. For this reason, it has become possible to achieve both the improvement of hot offset resistance, which has been a problem of adding a crystalline resin.
Further, since the amorphous resin having a high softening point is present in the vicinity of the amorphous resin having a low softening point which is plasticized by the action of the crystalline resin, the inorganic fine particles having a large particle diameter serving as a spacer are used in the toner. It is difficult to be embedded inside. For this reason, high transferability can be satisfied even in long-term image output.

<Resin A>
The resin A having a high softening point of the present invention has a softening point of 130 ° C. or more and 150 ° C. or less, and has a compatibility parameter SP (A) determined by the Fedors equation of 12.55 ≦ SP (A) ≦ 13.00. It is necessary to be.

When the softening point is in the above range, the toner can maintain a certain viscosity, and thus the hot offset resistance is improved. Further, when the softening point is in the above range, the viscosity of the resin A is in an appropriate range even with respect to the kneading temperature at the time of production, and the mixing property with the resin B having a low softening point is improved. can get.
When the softening point is lower than 130 ° C., the softening point of the toner is low, and the toner cannot have a certain viscosity, so that the hot offset resistance decreases. When the softening point is higher than 150 ° C., the viscosity of the resin A becomes high because the softening point is high with respect to the kneading temperature, the mixing property with the resin B having a low softening point is reduced, and the low-temperature fixing property and hot-resistance Offset properties and transfer properties decrease.

Further, when SP (A) is in the above range, since the SP value is sufficiently far from the crystalline resin, the resin A having a high softening point is not plasticized, so that the hot offset resistance is good. Becomes
When SP (A) is less than 12.55, the SP value becomes closer to the crystalline resin, and the resin A is also plasticized, so that the hot offset resistance decreases. When SP (A) is larger than 13.00, the difference in SP value from resin B is large, the mixing property with resin B is reduced, and the low-temperature fixability, hot offset resistance, and transferability are reduced. I do.

<Resin B>
The resin B having a low softening point of the present invention has a softening point of 80 ° C. or more and 95 ° C. or less, and has a compatibility parameter SP (B) determined by the Fedors equation of 11.80 ≦ SP (B) ≦ 12.40. It is necessary to be.

When the softening point is in the above-mentioned range, the toner can secure a certain viscosity, so that the low-temperature fixability is improved.
When the softening point is lower than 80 ° C., the softening point of the toner is lowered, so that the low-temperature fixability is improved. Further, when the softening point is higher than 95 ° C., the softening point of the toner is increased, so that the hot offset resistance and the transferability are improved, but the low-temperature fixability is reduced.

When SP (B) is in the above range, the resin B having a low softening point is plasticized since the SP value is sufficiently close to that of the crystalline resin, so that the low-temperature fixability is improved.
When SP (B) is less than 11.80, the difference between the SP value of the resin A and that of the resin A is large, the mixing property with the resin A is reduced, and the low-temperature fixability, hot offset resistance, and transferability are reduced. . When SP (B) is larger than 12.40, the SP value is farther than that of the crystalline resin, so that the plasticization of the resin B having a low softening point is reduced, so that the low-temperature fixability decreases.

<Resin C>
The resin C having a low softening point of the present invention has a softening point of 100 ° C. or more and 120 ° C. or less, and the compatibility parameter SP (C) determined by the Fedors equation is 12.40 ≦ SP (C) ≦ 12.55. It is necessary to be.

When the softening point is within the above range, the softening point of the resin C is a middle softening point of the resin A having a high softening point and the resin B having a low softening point, and the mixing property of the two resins is the best.
When the softening point is less than 100 ° C., the difference between the softening points of the resin A and the resin A becomes large, so that the mixing properties of the two resins are reduced, and the low-temperature fixability, hot offset resistance, and transferability are reduced. When the softening point is higher than 120 ° C., the difference between the softening points of the resin B and the resin B becomes large, so that the mixing properties of the two resins are reduced, and the low-temperature fixability, hot offset resistance, and transferability are reduced. .

  When SP (C) is in the above range, the SP value of resin C is a medium SP value of resin A having a high SP value and resin B having a low SP value, and the mixing property of the two types of resins is the best. become. When SP (C) is less than 12.40, the difference between the SP values of the resin A and the resin A becomes large, so that the mixing property of the two types of resins is reduced, and the low-temperature fixing property, hot offset resistance, and transferability are reduced. descend. When SP (C) is larger than 12.55, the difference in SP value from resin B is large, so that the mixing properties of the two resins are reduced, and the low-temperature fixability, hot offset resistance, and transferability are reduced. Decrease.

  Further, the resin A contains 70.0 mol% or more of a polyhydric alcohol unit derived from an ethylene oxide adduct of bisphenol A with respect to the total number of moles of the polyhydric alcohol unit, which is considered from the viewpoint of hot offset resistance. Is preferred. The reason is derived from the compatibility with the crystalline resin. The present inventors have clarified the relationship between the compatibility of bisphenol A, which is a typical alcohol monomer of the polyester resin, and the crystalline resin during the study. As a result, it was revealed that the ethylene oxide adduct of bisphenol A has low compatibility with the crystalline resin, and the use of the alcohol monomer of the resin A having a high softening point makes the resin A less likely to be plasticized. In addition, the hot offset resistance can be improved.

  Furthermore, from the viewpoint of low-temperature fixability, the resin B contains 70.0 mol% or more of a polyhydric alcohol unit derived from a propylene oxide adduct of bisphenol A based on the total number of moles of the polyhydric alcohol unit. preferable. The reason is also derived from the compatibility with the crystalline resin, and the propylene oxide adduct of bisphenol A has high compatibility with the crystalline resin and is used as the alcohol monomer of the resin B having a low softening point. B is further plasticized, so that low-temperature fixability can be improved.

Further, the resin C is
The polyhydric alcohol unit derived from the propylene oxide adduct of bisphenol A is contained in an amount of 40.0 mol% or more and 60.0 mol% or less based on the total number of moles of the polyhydric alcohol unit,
The low molecular weight fixing property and the hot offset resistance are such that the polyhydric alcohol unit derived from the ethylene oxide adduct of bisphenol A is contained in an amount of 40.0 mol% or more and 60.0 mol% or less based on the total number of moles of the polyhydric alcohol unit. It is preferable from the viewpoint of transferability and transferability.
When the monomer ratio of the resin C is within the above range, since the monomer ratio is a medium monomer ratio between the resin A and the resin B, the mixing property of the two types of resins can be improved.

  In addition, the average addition mole number of the propylene oxide adduct of the polyhydric alcohol unit derived from the bisphenol A propylene oxide adduct of the resin B is preferably from 2.5 to 3.0, from the viewpoint of low-temperature fixability. Is preferred. The reason is also derived from the compatibility with the crystalline resin. The present inventors have made studies and found that, among the propylene oxide adducts of bisphenol A, the higher the average number of moles of the propylene oxide adduct, the higher the compatibility with the crystalline resin. As a result, the resin B is further plasticized, so that the low-temperature fixability can be improved.

Further, it is preferable that SP (A) and SP (B) satisfy the relationship of the following (Equation 1) from the viewpoint of low-temperature fixability and hot offset resistance. When SP (A) and SP (B) satisfy the relationship of the following (Equation 1), the function separation between the resin A and the resin B with respect to the plasticization of the crystalline resin is performed in an optimal relationship, and therefore, the low-temperature fixing property And hot offset resistance are the best. In addition, the good mixing property of the two kinds of resins can be ensured, so that the transferring property is also in a good range.
0.65 ≦ SP (A) −SP (B) ≦ 1.00 (Equation 1)

  Further, the toner of the present invention preferably contains a styrene-based resin that finely disperses the crystalline resin from the viewpoint of low-temperature fixability. The crystalline polyester resin, which is the main component of the crystalline resin, is an ester compound of a long-chain hydrocarbon diol and a dicarboxylic acid. Polarity is located. Furthermore, since it is composed of a long-chain hydrocarbon diol and dicarboxylic acid, it tends to have a high affinity for an aliphatic hydrocarbon compound. By taking these into consideration, the present inventors can finely disperse the crystalline polyester resin by using a styrene-based resin graft-modified with an aliphatic hydrocarbon compound as the resin composition, and have a low-temperature fixing property. Successfully improved. Further, by using a styrene-based resin obtained by graft-modifying an aliphatic hydrocarbon compound, the dispersion of the release agent is improved, and the hot offset resistance is also improved.

  Further, it is preferable that the toner of the present invention is subjected to surface treatment using hot air, for example, using the surface treatment device shown in FIG. 1 from the viewpoint of transfer efficiency and low-temperature fixability. The hot air of the surface treatment device shown in FIG. 1 instantaneously melts the toner, and then is rapidly cooled. As a result, the crystalline polyester resin can be maintained in a state compatible with the binder resin without being recrystallized, so that the maximum plasticizing effect can be obtained and the low-temperature fixability can be improved. The crystalline polyester resin present can be eliminated. Therefore, it is possible to reduce the embedding of the inorganic fine particles having a large particle diameter serving as the spacer into the toner.

[Amorphous resin]
It is necessary that the amorphous resin used in the toner of the present invention contains a polyester resin as a main component. The monomers used for the polyester unit of the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trivalent or higher carboxylic acids), acid anhydrides thereof, and lower acids thereof. Alkyl esters are used. Here, when producing a branched polymer, it is effective to partially crosslink in the molecule of the amorphous resin, and for this purpose, it is preferable to use a trifunctional or higher polyfunctional compound. Therefore, it is preferable that the raw material monomer of the polyester unit contains a trivalent or higher carboxylic acid, an acid anhydride thereof or a lower alkyl ester thereof, and / or a trivalent or higher alcohol.

As the polyhydric alcohol monomer used for the polyester unit of the polyester resin, the following polyhydric alcohol monomers can be used.
Examples of the dihydric alcohol component include the following.
Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol , 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenols represented by the formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
式（Ｂ）で示されるジオール類；

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)
Diols of formula (B);

Examples of the trivalent or higher alcohol component include the following.
Sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripetaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol , 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.
Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination of two or more.

As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.
Examples of the divalent carboxylic acid component include the following.
Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid , N-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include the following.
1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid , Empol trimer acids, their anhydrides or their lower alkyl esters.
Among these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is particularly preferably used because it is inexpensive and the reaction control is easy. These divalent carboxylic acids and the like and trivalent or more carboxylic acids can be used alone or in combination of two or more.

The method for producing the polyester unit of the present invention is not particularly limited, and a known method can be used.
For example, the above-mentioned alcohol monomer and carboxylic acid monomer are mixed and polymerized through an esterification reaction or transesterification reaction and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 290 ° C. In the polymerization of the polyester unit, for example, a polymerization catalyst such as a titanium catalyst, a tin catalyst, zinc acetate, antimony trioxide, and germanium dioxide can be used. In particular, the amorphous resin of the present invention is more preferably a polyester unit polymerized using a tin-based catalyst.

The amorphous resin used in the toner of the present invention may be a hybrid resin containing another resin component as long as the resin is a polyester resin as a main component. For example, a hybrid resin of a polyester resin and a vinyl resin may be used. As a method for obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin such as a hybrid resin, the following method is preferable.
A method in which a polymer containing a monomer component capable of reacting with each of a vinyl resin, a vinyl copolymer unit and a polyester resin is present, and one or both of the resins are polymerized.

  Examples of the monomer constituting the polyester resin component that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, and anhydrides thereof. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

In the present invention, if a polyester resin is the main component as the binder resin, various resin compounds conventionally known as binder resins can be used in addition to the above-mentioned vinyl resin. Examples of such a resin compound include the following.
Phenol resin, natural resin modified phenolic resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene Resin, coumaroindene resin, petroleum resin.

  The amorphous resin of the present invention is used by mixing a resin A having a low softening point, a resin B having a high softening point, and a resin C having a medium softening point. The content ratio (A / B) of the resin A and the resin B is preferably 10/90 or more and 60/40 or less on a mass basis from the viewpoint of low-temperature fixability and hot offset resistance. Further, from the viewpoint of the mixing property between the resin A and the resin B, the amount of the resin C is preferably 5% by mass or more and 20% by mass or less in the amorphous resin.

  The resin A having a high softening point preferably has a peak molecular weight of 9000 or more and 12000 or less from the viewpoint of hot offset resistance. The acid value of the resin A is preferably from 15 mgKOH / g to 30 mgKOH / g from the viewpoint of charge stability in a high-temperature and high-humidity environment. Further, the hydroxyl value of the resin A is preferably from 15 mgKOH / g to 30 mgKOH / g from the viewpoint of storage stability.

  The resin B having a low softening point preferably has a peak molecular weight of 4,000 to 8,000 from the viewpoint of low-temperature fixability. Further, the acid value of the resin B is preferably 1 mgKOH / g or more and 10 mgKOH / g or less from the viewpoint of charging stability under a high temperature and high humidity environment. Further, the hydroxyl value of the resin B is preferably from 15 mgKOH / g to 30 mgKOH / g from the viewpoint of storage stability.

  It is preferable that the peak molecular weight of the resin C having a middle softening point is 5,000 or more and 9000 or less from the viewpoint of the miscibility of the two kinds of resins. The acid value of the resin C is preferably 1 mgKOH / g or more and 15 mgKOH / g or less from the viewpoint of charge stability in a high-temperature and high-humidity environment. Further, the hydroxyl value of the resin C is preferably from 15 mgKOH / g to 30 mgKOH / g from the viewpoint of storage stability.

[Crystalline resin]
The crystalline resin in the present invention is a resin for which an endothermic peak is observed in differential scanning calorimetry (DSC).
The crystalline resin used in the toner of the present invention must contain a polyester resin as a main component.
In the toner of the present invention, the crystalline polyester contained in the toner particles includes a monomer composition containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components. It is obtained by a condensation reaction.
Among them, as a result of intensive studies by the present inventors, an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms are preferable from the viewpoint of low-temperature fixability and storage stability.

The use of crystalline polyester improves the low-temperature fixability of the toner. The reason is that the binder resin and the crystalline polyester are compatible, the spacing between the molecular chains of the binder resin is widened, and the intermolecular force is weakened, thereby greatly lowering the glass transition temperature (Tg) and reducing the melt viscosity. Derived from lowering.
Therefore, low-temperature fixability tends to be improved by increasing the compatibility between the binder resin and the crystalline polyester.
Then, in order to increase the compatibility between the binder resin and the crystalline polyester, the number of carbon atoms of the aliphatic diol and / or the aliphatic dicarboxylic acid constituting the crystalline polyester is reduced, and the ester group concentration is increased. The polarity will be increased.

On the other hand, it is necessary to ensure the storability of the toner whose Tg has been significantly reduced in use or transportation under a high temperature and high humidity environment. For that purpose, when the toner is exposed in such an environment, it is necessary to recrystallize the crystalline polyester in the compatible toner to return the Tg of the toner to the Tg of the binder resin. .
Here, when the ester group concentration of the crystalline polyester is high and the compatibility between the binder resin and the crystalline polyester is too high, it is difficult to recrystallize the crystalline polyester, and the storage stability of the toner decreases. Will be.
From the above, it is preferable to use an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms as the monomer configuration of the crystalline polyester capable of achieving both low-temperature fixability and storage stability. I found it.

The aliphatic diol having 2 to 22 carbon atoms (more preferably, 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably, linear) aliphatic diol. Are preferably exemplified.
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentane Examples include methylene glycol, 1,6-hexanediol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Among these, linear aliphatic, α, ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol and 1,6-hexanediol.
Of the above alcohol components, preferably at least 50% by mass, more preferably at least 70% by mass is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

In the present invention, a polyhydric alcohol monomer other than the above-mentioned aliphatic diol may be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropyleneated bisphenol A; and 1,4-cyclohexanedimethanol. Further, among the polyhydric alcohol monomers, examples of the trihydric or higher polyhydric alcohol monomer include the following.
Aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methyl Aliphatic alcohols such as propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

Further, in the present invention, a monovalent alcohol may be used to such an extent that the properties of the crystalline polyester are not impaired. Examples of the monohydric alcohol include mono-alcohols such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a linear (more preferably linear) aliphatic dicarboxylic acid. . Specific examples include the following.
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, spearic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid Acids, mesaconic acid, citraconic acid, itaconic acid, and those obtained by hydrolyzing acid anhydrides or lower alkyl esters thereof.
In the present invention, among the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.

In the present invention, a polyvalent carboxylic acid other than the above-mentioned aliphatic dicarboxylic acid having 2 to 22 carbon atoms may be used. Among the other polyvalent carboxylic acid monomers, examples of the divalent carboxylic acid include the following.
Aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid; acid anhydrides and lower alkyl esters thereof.
Further, among the other carboxylic acid monomers, examples of the trivalent or higher polyvalent carboxylic acid include the following.
Aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid; Aliphatic carboxylic acids such as -butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives thereof such as acid anhydrides or lower alkyl esters .

  Further, in the present invention, a monovalent carboxylic acid may be contained so as not to impair the properties of the crystalline polyester. Examples of the monovalent carboxylic acid include monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, and octanoic acid. Acids.

  Further, the crystalline polyester resin of the present invention is a crystalline polyester resin in which one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids having 10 to 20 carbon atoms and aliphatic monoalcohols are condensed at the ends of molecular chains. It is preferably a conductive polyester resin. Generally, in recrystallization of a crystalline polyester, crystals grow from a crystal nucleus as a starting point. Therefore, by giving one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids having 10 to 20 carbon atoms and aliphatic monoalcohols to the ends of the molecular chains, the nuclei become crystal nuclei and recrystallize. Since storage can be promoted, storage stability is improved.

Further, when the number of carbon atoms is in the above range, it is easy to condense to the terminal of the molecular chain, and it is not present as a free monomer. Further, when the number of carbon atoms is in the above range, the compatibility between the crystalline polyester and the binder resin is not impaired, so that it is preferable from the viewpoint of low-temperature fixability.
Further, the content of such an aliphatic compound is preferably 1.0 mol% or more and 10.0 mol% or less, and preferably 4.0 mol% or more and 8.0 mol% or less with respect to the raw material monomer of the crystalline polyester resin. Is more preferable. When the content of the aliphatic compound is in the above range, an appropriate amount of crystal nuclei can be present without impairing the low-temperature fixability, which is preferable.

Examples of the aliphatic monocarboxylic acid having 10 to 20 carbon atoms include the following.
Capric acid (decanoic acid), undecylic acid, lauric acid (dodecanoic acid), tridecylic acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid) , Nonadecyl acid, arachidic acid (icosanoic acid).

The aliphatic monoalcohol having 10 to 20 carbon atoms includes the following.
Caprylic alcohol (decanol), undecanol, lauryl alcohol (dodecanol), tridecanol, myristyl alcohol (tetradecanol), pentadecanol, palmityl alcohol (hexadecanol), margaryl alcohol (heptadecanol), stearyl alcohol (octayl) Decanol), nonadecanol, arachidyl alcohol (icosanol).

In the present invention, the amount of the crystalline polyester resin used is preferably 3 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the amorphous resin from the viewpoint of low-temperature fixability and chargeability in a high-temperature and high-humidity environment. .
The crystalline polyester in the present invention can be produced according to a usual polyester synthesis method. For example, after the carboxylic acid monomer and the alcohol monomer are subjected to an esterification reaction or a transesterification reaction, a polycondensation reaction is carried out under a reduced pressure or by introducing a nitrogen gas according to a conventional method to obtain a crystallinity. Polyester can be obtained. Thereafter, by further adding the above-mentioned aliphatic compound and performing an esterification reaction, a desired crystalline polyester can be obtained.

The above-mentioned esterification or transesterification reaction can be carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate or magnesium acetate, if necessary.
In addition, the polycondensation reaction can be performed using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. . The polymerization temperature and the amount of the catalyst are not particularly limited, and may be appropriately determined.
In an esterification or transesterification reaction or polycondensation reaction,
In order to increase the strength of the obtained crystalline polyester, all monomers are mixed at once,
In order to reduce low molecular weight components, a method of first reacting a divalent monomer and then adding and reacting a trivalent or higher monomer may be used.

[Styrene resin graft-modified with aliphatic hydrocarbon compound]
The toner according to the invention more preferably contains a styrene resin graft-modified with an aliphatic hydrocarbon compound from the viewpoint of low-temperature fixability.
The content of the styrene resin graft-modified with the aliphatic hydrocarbon compound is preferably from 1.0 part by mass to 15 parts by mass with respect to 100 parts by mass of the amorphous resin. When the content is in this range, fine dispersion of the crystalline polyester in the amorphous resin by the styrene resin graft-modified with the aliphatic hydrocarbon compound is considered to be performed efficiently.

Further, as a constituent monomer unit of the styrene resin, it is preferable to include a monomer unit having a functional unit containing a nitrogen atom, such as acrylonitrile or methacrylonitrile. By containing a monomer unit having a functional unit containing a nitrogen atom as a constituent monomer unit, it is considered that the affinity with the crystalline polyester resin is increased and the effect of finely dispersing the crystalline polyester resin is enhanced.
Regarding the styrene-based resin graft-modified with an aliphatic hydrocarbon compound, the polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins may be used. it can. Particularly, polyethylene and polypropylene are preferably used.

Examples of the monomer having a vinyl group include the following.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene Styrene units such as styrene and its derivatives.

Amino group-containing α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl units containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; unsaturated such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride Dibasic acid anhydride: methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinate Half esters of unsaturated dibasic acids such as methyl half ester of methyl fumarate, methyl half ester of fumaric acid and methyl half ester of mesaconic acid; unsaturated dibasic acid esters of dimethyl maleic acid and dimethyl fumaric acid; acrylic acid and methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride; anhydride of the α, β-unsaturated acid and lower fatty acid A vinyl unit containing a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, anhydrides thereof, and monoesters thereof.

  Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) Hexyl) Vinyl units containing a hydroxy group such as styrene.

Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid-2- Ester units composed of acrylates such as acrylates such as chloroethyl and phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Ester units composed of methacrylic esters such as α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;
The graft polymer obtained by graft-polymerizing a vinyl-based monomer to the polyolefin used in the present invention is obtained by a known method such as a reaction between these polymers described above or a reaction between a monomer of one polymer and another polymer. Obtainable.

[Release agent]
Examples of the wax used in the toner of the present invention include the following.
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; hydrocarbon wax oxides such as oxidized polyethylene wax or block copolymers thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.

Further, the following may be mentioned.
Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinaric acid; Saturated alcohols such as silalcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, meri Esters with alcohols such as silalcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylenebislauric amide, hexamethylenebisstearic acid amide; ethylenebisoleic amide, hexamethylenebisoleic amide, N, N'dioleyladipamide, N, N'dioleyl Unsaturated fatty acid amides such as sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N 'distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate and the like Aliphatic metal salts (commonly referred to as metallic soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride And polyvalent alco Le portions ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferred from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.
In the present invention, the wax is preferably used in an amount of 1 to 20 parts by mass per 100 parts by mass of the binder resin.
In the endothermic curve at the time of temperature increase measured by a differential scanning calorimeter (DSC), the maximum endothermic peak temperature of the wax is preferably 45 ° C. or more and 140 ° C. or less. When the peak temperature of the maximum endothermic peak of the wax is within the above range, it is preferable because both the storage stability and the hot offset resistance of the toner can be achieved.

[Colorant]
The following colorants can be included in the toner.
Examples of the black colorant include carbon black; a black color tone using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.

  The pigments for magenta toner include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; I. Butt Red 1,2,10,13,15,23,29,35.

  The dyes for magenta toner include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse Red 9; I. Solvent violet 8, 13, 14, 21, 27; I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the pigment for cyan toner include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat blue 6; I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. Solvent Blue 70.

Examples of the yellow toner pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, C. 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
Dyes for yellow toner include C.I. I. Solvent Yellow 162.
The colorant is preferably used in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the binder resin.

[Charge control agent]
The toner may contain a charge control agent as needed. As the charge control agent contained in the toner, a known charge control agent can be used. In particular, a metal compound of an aromatic carboxylic acid which is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.
Examples of the negative charge control agent include the following.
Salicylic acid metal compound, naphthoic acid metal compound, dicarboxylic acid metal compound,
Polymer type compound having sulfonic acid or carboxylic acid in the side chain, polymer type compound having sulfonic acid salt or sulfonic acid ester in the side chain, polymer type compound having carboxylic acid salt or carboxylic acid ester in the side chain ,
Boron compounds, urea compounds, silicon compounds, calixarenes.
Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound, and an imidazole compound.
The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the binder resin.

[Inorganic particles]
The toner of the present invention may contain inorganic fine particles as necessary. The inorganic fine particles may be internally added to the toner particles, or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powder such as silica, titanium oxide, and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As the external additive for improving flowability, the specific surface area of ^{50 m} 2 / g or more 400 meters ² / g or less of the inorganic fine powder is preferred, in order to stabilize the durability, the specific surface area of ^{10 m} 2 / g It is preferable that the inorganic fine powder is at least 50 m ² / g or less. In order to achieve both improvement in fluidity and stabilization of durability, an inorganic fine powder having a specific surface area in the above range may be used in combination.
The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass based on 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

[Developer]
Although the toner of the present invention can be used as a one-component developer, it can be mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility. Is preferred in that is obtained.
Examples of the magnetic carrier include the following.
A magnetic material-dispersed resin carrier (a so-called resin carrier) containing a magnetic material or a magnetic material and a binder resin holding the magnetic material in a dispersed state.
The following are examples of the magnetic material.
Iron powder with oxidized surface or unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, alloy particles thereof, and oxide particles , Ferrite and so on.
When the toner of the present invention is used as a two-component developer by mixing it with a magnetic carrier, the carrier mixing ratio at that time is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the two-component developer. When the content is 4% by mass or more and 13% by mass or less, usually good results are obtained.

[Production method]
As a method for producing the toner particles, it is necessary to melt-knead the binder resin, the releasing agent, the colorant, and the crystalline polyester. Pulverization is preferred.
Hereinafter, the procedure for producing the toner by the pulverization method will be described.
In the raw material mixing step, as a material constituting the toner particles, for example, a predetermined amount of other components such as a binder resin, a release agent, a colorant, a crystalline polyester, and a charge control agent are weighed and compounded. Mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.).

  Next, the mixed materials are melt-kneaded to disperse wax and the like in the binder resin. In the melt-kneading process, a batch-type kneader such as a pressure kneader or a Banbury mixer or a continuous-type kneader can be used, and a single-screw or twin-screw extruder is mainly used because of its superiority in continuous production. ing. For example, a KTK type twin screw extruder (manufactured by Kobe Steel Ltd.), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Co., Ltd.), and a twin screw extruder (K • K-Kneader (manufactured by Bus) and Kneedex (manufactured by Nippon Coke Industry Co., Ltd.). Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like, and cooled with water or the like in a cooling step.

Next, the cooled product of the resin composition is crushed to a desired particle size in a crushing step. In the pulverizing step, for example, after coarsely pulverizing with a pulverizer such as a crusher, a hammer mill, and a feather mill, further, for example, a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.) and a super rotor (manufactured by Nisshin Engineering Co., Ltd.) And finely pulverized by a turbo mill (manufactured by Freund Turbo Co., Ltd.) or an air jet pulverizer.
Thereafter, if necessary, an inertial classification type elbow jet (produced by Nittetsu Mining Co., Ltd.), a centrifugal classification type turboplex (produced by Hosokawa Micron Corp.), a TSP separator (produced by Hosokawa Micron Corp.), a faculty (hosokawa micron) Classification using a classifier or a sieve classifier (manufactured by Co., Ltd.).

Thereafter, surface treatment of the toner particles by heating is performed to increase the circularity of the toner.
For example, the surface treatment can be performed by hot air using the surface treatment apparatus shown in FIG.
The mixture quantitatively supplied by the raw material constant supply means 101 is guided by the compressed gas adjusted by the compressed gas adjustment means 102 to the introduction pipe 103 installed on the vertical line of the raw material supply means. The mixture that has passed through the introduction pipe is evenly dispersed by a conical protruding member 104 provided at the center of the raw material supply means, and is guided to an eight-way supply pipe 105 that spreads radially to perform a heat treatment in a processing chamber 106. Is led to.

At this time, the flow of the mixture supplied to the processing chamber is regulated by regulating means 109 provided in the processing chamber for regulating the flow of the mixture. Therefore, the mixture supplied to the processing chamber is heat-treated while rotating in the processing chamber, and then cooled.
Hot air for heat-treating the supplied mixture is supplied from the hot-air supply unit 107, and the hot air is spirally swirled into the processing chamber by the swirling member 113 for swirling the hot air. As the configuration, the turning member 113 for turning the hot air has a plurality of blades, and the turning of the hot air can be controlled by the number and the angle of the blades. The hot air supplied into the processing chamber preferably has a temperature at the outlet of the hot air supply unit 107 of 100 ° C to 300 ° C. When the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly perform a spheroidizing process on the toner particles while suppressing fusion and coalescence of the toner particles due to excessive heating of the mixture. Become.

Further, the heat-treated heat-treated toner particles are cooled by cold air supplied from the cold air supply means 108, and the temperature supplied from the cold air supply means 108 is preferably -20C to 30C. When the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and the fusion and coalescence of the heat-treated toner particles can be suppressed without impeding the uniform spheroidization of the mixture. be able to. It is preferable that the absolute moisture content of the cold air is 0.5 g / m ³ or more and 15.0 g / m ³ or less.
Next, the cooled heat-treated toner particles are collected by the collecting means 110 at the lower end of the processing chamber. In addition, a blower (not shown) is provided at the end of the collecting means, and is configured to be suction-conveyed by the blower.

  In addition, the powder particle supply port 114 is provided so that the turning direction of the supplied mixture and the turning direction of the hot air are the same, and the collection unit 110 of the surface treatment device is configured to collect the turned powder particles. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cool air supplied from the cool air supply means 108 is configured to be supplied horizontally and tangentially from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The turning direction of the toner supplied from the powder supply port, the turning direction of the cool air supplied from the cool air supply means, and the turning direction of the hot air supplied from the hot air supply means are all the same. Therefore, turbulence does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner, and the dispersibility of the toner is further improved. Can be obtained.

When the average circularity of the toner is 0.950 or more and 0.980 or less, it is preferable because transferability is improved and cleaning performance is compatible.
Further, if necessary, an external additive is externally added to the surface of the toner particles. As a method of externally adding the external additive, there is a method in which a predetermined amount of the classified toner and various known external additives are blended, and the mixture is stirred and mixed using the following mixing apparatus as an external additive.
Double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.), and novirta (manufactured by Hosokawa Micron Corporation).
Methods for measuring various physical properties of the toner and the raw materials will be described below.

[Measurement of molecular weight of crystalline resin by GPC]
First, the crystalline polyester resin is dissolved in o-dichlorobenzene over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maeshoridisk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.

Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H HT 7.8 cmI. D × 30cm2 (Tosoh Corporation)
Detector: High temperature RI
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.05% ionol added)
Flow rate: 1.0 mL / min Sample: Inject 0.4 mL of a 0.1% sample. Under the above conditions, the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. Further, it is calculated by converting into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

[Measurement of molecular weight of amorphous resin by GPC]
The molecular weight distribution of the THF-soluble component of the resin is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maeshoridisk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.

Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
When calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-20, 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation).

[Method of calculating SP value of amorphous resin by Fedors equation]
The SP value of the amorphous resin was determined by the Fedors equation. The SP value is defined by the square root of the cohesive energy density as in (Equation 2).
SP = (ΔE / V) ^1/2 = [Δei / Δvi] ^1/2 (Equation 2)
ΔE: Cohesive energy (evaporation energy)
V: molar molecular volume of the solvent Δei: evaporation energy of the atom or atomic group of the i component Δvi: molar volume of the atom or atomic group of the i component V and ΔE used in calculating the SP value of the amorphous resin of the present invention. Are shown in Table 1.

For example, hexanediol is composed of the atomic group {(-OH) × 2 + (— CH2) × 6}, and the calculated SP value is obtained by the following equation.
δi = [Δei / Δvi] ^1/2 = [{(5220) × 2 + (1180) × 6} / {(13) × 2 + (16.1) × 6}] ^1/2
The SP value (δi) is 11.95.
Table 2 shows the SP value of each monomer of the resin A1 and the SP value of the resin A1 used in Example 1.

[Method for Measuring Softening Point of Amorphous Resin, Resin Composition, Toner]
The measurement of the softening point of the resin is carried out using a capillary rheometer of constant load extrusion method “Flow tester CFT-500D” (manufactured by Shimadzu Corporation) in accordance with the manual attached to the apparatus. In this device, while applying a constant load with a piston from the top of the measurement sample, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is extruded from the die at the bottom of the cylinder, and the piston descends at this time. A flow curve showing the relationship between temperature and temperature can be obtained.

In the present invention, the “melting temperature in the 法 method” described in the manual attached to the “flow characteristic evaluation apparatus flow tester CFT-500D” is defined as the softening point. The melting temperature in the 1/2 method is calculated as follows. First, the difference between the piston descending amount Smax at the time when the outflow ends and the piston descending amount Smin at the time when the outflow starts is determined (this is defined as X. X = (Smax−Smin) / 2). The temperature of the flow curve when the piston descends X in the flow curve is the melting temperature in the 1/2 method.
The measurement sample was prepared by compressing about 1.0 g of the resin at about 10 MPa for about 60 seconds in a 25 ° C. environment using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.). A column having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.

Test mode: Temperature rise method starting temperature: 50 ° C
Ultimate temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C./min. Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

[Measurement of glass transition temperature (Tg) of amorphous resin and toner]
[Measurement of melting peak temperature (Tp) of crystalline resin]
The glass transition temperature of the resin is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) according to ASTM D3418-82.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.
Specifically, about 3 mg of the resin or toner is precisely weighed, placed in an aluminum pan, and measured using an empty aluminum pan as a reference under the following conditions.

Heating rate: 10 ° C / min Measurement start temperature: 30 ° C
Measurement end temperature: 180 ° C
The measurement is performed at a rate of temperature increase of 10 ° C./min within a measurement range of 30 to 180 ° C. The temperature is raised once to 180 ° C., held for 10 minutes, then lowered to 30 ° C., and then raised again. In the second heating process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. The intersection between the line at the midpoint of the baseline before and after the specific heat change and the differential heat curve at this time is defined as the glass transition temperature (Tg) of the resin. Further, the temperature at which the maximum endothermic peak of the temperature-endothermic curve in the temperature range of 60 to 90 ° C. is defined as the melting peak temperature (Tp).

[Measurement of endothermic peak derived from crystalline resin from toner by DSC]
The measurement of the endothermic peak derived from the crystalline resin from the toner is performed using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments) in accordance with ASTM D3418-82.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium.
Specifically, about 3 mg of the toner is precisely weighed, placed in an aluminum pan, and measured using an empty aluminum pan as a reference under the following conditions.

Heating rate: 10 ° C / min Measurement start temperature: 30 ° C
Measurement end temperature: 180 ° C
Holding temperature: 50 ° C
The measurement is performed at a rate of temperature increase of 10 ° C./min within a measurement range of 30 to 180 ° C. The temperature is raised once to 50 ° C. and maintained for 3 days, then lowered to 30 ° C., and then raised again. In the second heating process, an endothermic peak is obtained from the baseline in the temperature range of 30 to 100 ° C. If the endothermic peak at this time can be separated from the endothermic peak derived from the enthalpy relaxation or the release agent, the endothermic peak is regarded as the endothermic peak derived from the crystalline resin.

When the obtained endothermic peak cannot be separated from the endothermic peak derived from the enthalpy relaxation or the release agent, or when the compatibility between the amorphous resin and the crystalline resin is high and does not appear as an endothermic peak, The measurement is performed after separating the crystalline resin from the toner using the difference in solubility of the crystalline resin.
The separation of the crystalline resin from the toner is performed in the following procedure.
First separation: A toner is dissolved in methyl ethyl ketone (hereinafter also referred to as “MEK”) at a temperature of 23 ° C., and a soluble (amorphous resin) and an insoluble (a crystalline resin, a release agent, a colorant, Inorganic particles).
Second separation: Insoluble matter (crystalline resin, release agent, colorant, inorganic particles) obtained in the first separation is dissolved in MEK at a temperature of 100 ° C., and soluble matter (crystalline resin, release agent) ) And insolubles (colorant, inorganic particles).
Third separation: The soluble matter (crystalline resin, release agent) obtained in the second separation is dissolved in chloroform at a temperature of 23 ° C., and the soluble matter (crystalline resin) and the insoluble matter (release agent) are dissolved. Is separated.
By performing DSC measurement of the obtained soluble component (crystalline resin), an endothermic peak derived from the crystalline resin can be measured.

[Method of Measuring Weight Average Particle Diameter (D4) of Toner Particles]
The weight-average particle diameter (D4) of the toner particles was measured with a precision particle size distribution analyzer “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electric resistance method. The number of effective measurement channels is 25,000 using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data. Then, the measured data is analyzed and calculated.
The electrolytic aqueous solution used for the measurement may be a solution prepared by dissolving a special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.). .

Before performing the measurement and analysis, the dedicated software is set as follows.
In the “Change standard measurement method (SOM) screen” of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter (Manufactured by Co., Ltd.). The threshold and the noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check mark is placed in the flash of the aperture tube after the measurement.
On the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measuring method is as follows.

(1) About 200 mL of the aqueous electrolytic solution is placed in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 mL of the electrolytic aqueous solution is placed in a 100-mL flat bottom beaker made of glass, and about 0.3 mL of a diluent obtained by diluting the dispersant 3 times by mass with ion-exchanged water is added thereto.
"Contaminone N" as a dispersant (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument at pH 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) Use

(3) Two oscillators having an oscillation frequency of 50 kHz are built in a state shifted by 180 degrees, and a predetermined amount of ion-exchanged water is put in a water tank of an ultrasonic disperser having an electric output of 120 W. About 2 mL of Contaminone N is added.
"Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) is used as an ultrasonic disperser.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the aqueous electrolytic solution in the beaker becomes maximum.

(5) About 10 mg of the toner is added little by little to the aqueous electrolytic solution in the beaker of the above (4) in a state where the aqueous electrolytic solution is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the temperature of the water in the water tank is 10 ° C. or more and 40 ° C. or less.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte aqueous solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) Analyze the measured data with the dedicated software attached to the device, and calculate the weight average particle size (D4). The “average diameter” on the analysis / volume statistical value (arithmetic average) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

[Method of measuring average circularity of toner]
The average circularity of the toner is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration work.
The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to a flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow forms a flat flow between the sheath liquids. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, so that the flowing particles can be captured as a still image. Further, since the flow is flat, the image is captured in a focused state. The particle image is captured by a CCD camera, and the captured image is processed at an image processing resolution of 512 × 512 pixels (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted. Are measured.

Next, a circle equivalent diameter and a circularity are determined using the projection area S and the perimeter L. The circle equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the circle equivalent diameter by the circumference of the particle projection image. And is calculated by the following equation.
Circularity C = {2 × (π × S) ^1/2 } / L
When the particle image is circular, the circularity is 1.000, and the circularity becomes smaller as the degree of unevenness on the outer periphery of the particle image increases. After calculating the degree of circularity of each particle, the range of the degree of circularity of 0.200 to 1.000 is divided into 800, and the arithmetic mean of the obtained degrees of circularity is calculated, and the value is defined as the average degree of circularity.

  The specific measuring method is as follows. First, about 20 mL of ion-exchanged water from which impurity solids and the like have been removed in advance is placed in a glass container. A 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 consisting of a nonionic surfactant, an anionic surfactant and an organic builder was used as a dispersant in the product, Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 mL of a diluent is added. Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or more and 40 ° C. or less. As the ultrasonic disperser, a desktop ultrasonic washer disperser having an oscillation frequency of 50 kHz and an electric output of 150 W (for example, "VS-150" (manufactured by Vervocreer Co., Ltd.)) was used. A fixed amount of ion-exchanged water is added, and about 2 mL of the contaminone N is added to the water tank.

  For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3,000 toner particles are measured in the HPF measurement mode in the total count mode. By setting the binarization threshold at the time of particle analysis to 85% and designating the analysis particle diameter, the number ratio (%) of particles in the range and the average circularity can be calculated. The average circularity of the toner was 1.98 μm or more and 39.96 μm or less, and the average circularity of the toner was determined.

In the measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) with ion-exchanged water before the start of the measurement. Thereafter, it is preferable to perform the focus adjustment every two hours from the start of the measurement.
In the examples of the present application, a flow-type particle image analyzer that has been calibrated by Sysmex Corporation and has been issued a calibration certificate issued by Sysmex Corporation was used. The measurement was performed under the measurement and analysis conditions when the calibration certificate was obtained, except that the analysis particle diameter was limited to the circle equivalent diameter of 1.98 μm or more and less than 39.69 μm.

<Production Example of Resin A1 with High Softening Point>
-Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.2 parts by mass (0.20 mol; 100.0 mol% based on the total mol number of polyhydric alcohol)
·Terephthalic acid:
13.2 parts by mass (0.08 mol; 48.0 mol% based on the total number of moles of polycarboxylic acid)
・ Adipic acid:
8.2 parts by mass (0.06 mol; 34.0 mol% based on the total number of mols of polycarboxylic acid)
・ Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass

The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introduction pipe, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was performed for 2 hours while stirring at a temperature of 200 ° C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, and after maintaining for 1 hour, it was cooled to 160 ° C. and returned to the atmospheric pressure (first reaction step).

・ Trimellitic acid:
6.3 parts by mass (0.03 mol; 18.0 mol% based on the total number of moles of polycarboxylic acid)
-Tert-butyl catechol (polymerization inhibitor): 0.1 parts by mass Then, the above-mentioned materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160 ° C. After confirming that the softening point measured according to −86 reached a temperature of 140 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, a resin A1 was obtained.
The obtained resin A1 had a peak molecular weight Mp10000, a softening point Tm of 140 ° C., a glass transition temperature Tg of 60 ° C., and SP (A) of 12.74.

<Production Examples of Resins A2 to A11 with High Softening Point>
In the production example of the resin A1, the monomers and the number of parts by mass of the polyhydric alcohol component and / or the polycarboxylic acid component in the first reaction step were changed as shown in Table 3, and the monomers in the second reaction step were changed. And the number of parts by mass were changed as shown in Table 3. Except for these, the reaction was carried out in the same manner as in the production example of resin A1, and resins A2 to A11 were obtained. Table 3 shows the physical properties of Resins A2 to A11.

<Production example of resin B1 having low softening point>
-Polyoxypropylene (2.8) -2,2-bis (4-hydroxyphenyl) propane: 76.6 parts by mass (0.17 mol; 100.0 mol% based on the total mol number of polyhydric alcohol)
·Terephthalic acid:
17.4 parts by mass (0.10 mol; 72.0 mol% based on the total number of moles of polycarboxylic acid)
・ Adipic acid:
6.0 parts by mass (0.04 mol; 28.0 mol% based on the total number of moles of polycarboxylic acid)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above-mentioned materials were weighed in a cooling tube, a stirrer, a nitrogen introducing tube, and a reaction vessel equipped with a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction tank was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180 ° C., and returned to the atmospheric pressure (first reaction step).

-Tert-butyl catechol (polymerization inhibitor): 0.1 parts by mass After that, the above-mentioned materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180 ° C. After confirming that the softening point measured according to −86 reached a temperature of 90 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, a resin B1 was obtained.
The obtained resin B1 had a peak molecular weight Mp7000, a softening point Tm of 90 ° C, a glass transition temperature Tg of 54 ° C, and SP (B) of 12.05.

<Production Example of Resins B2 to B14 with Low Softening Point>
In the production example of the resin B1, the monomers and parts by mass of the polyhydric alcohol component and / or polycarboxylic acid component in the first reaction step and the reaction time were changed as shown in Table 4, and the temperature of the second reaction step was changed. And time were changed as shown in Table 4. Except for these, the reaction was carried out in the same manner as in the production example of resin B1, and resins B2 to B14 were obtained. Table 4 shows the physical properties of Resins B2 to B14.

<Production Example of Resin C1 with Medium Softening Point>
-Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 38.2 parts by mass (0.10 mol; 50.0 mol% based on the total mol number of polyhydric alcohol)
-Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 35.2 parts by mass (0.10 mol; 50.0 mol% based on the total mol number of polyhydric alcohol)
·Terephthalic acid:
16.1 parts by mass (0.10 mol; 60.0 mol% based on the total number of moles of polycarboxylic acid)
・ Adipic acid:
7.1 parts by mass (0.05 mol; 30.0 mol% based on the total mol number of polycarboxylic acid)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above-mentioned materials were weighed in a cooling tube, a stirrer, a nitrogen introducing tube, and a reaction vessel equipped with a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was performed for 3 hours while stirring at a temperature of 200 ° C.
Furthermore, the pressure in the reaction tank was lowered to 8.3 kPa, and after maintaining for 1 hour, it was cooled to 170 ° C. and returned to the atmospheric pressure (first reaction step).

-Trimellitic anhydride: 3.4 parts by mass (0.02 mol; 10.0 mol% based on the total number of moles of polycarboxylic acid)
-Tert-butylcatechol (polymerization inhibitor): 0.1 parts by mass After that, the above-mentioned materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 10 hours while maintaining the temperature at 170 ° C, to obtain ASTM D36. After confirming that the softening point measured according to −86 reached a temperature of 110 ° C., the temperature was lowered to stop the reaction (second reaction step). Thus, a resin C1 was obtained.
The obtained resin C1 had a peak molecular weight Mp8000, a softening point Tm of 110 ° C, a glass transition temperature Tg of 57 ° C, and SP (C) of 12.47.

<Production Example of Resins C2 to C5 with Medium Softening Point>
In the production example of the resin C1, the monomers and the number of parts by mass of the polyhydric alcohol component and / or the polycarboxylic acid component in the first reaction step were changed as shown in Table 5, and the monomers in the second reaction step were changed. And the number of parts by mass were changed as shown in Table 5. Except for these, the reaction was carried out in the same manner as in the production example of resin C1, and resins C2 to C5 were obtained. Table 5 shows the physical properties of Resins C2 to C5.

<Production Example of Crystalline Resin D1>
・ Hexanediol:
34.5 parts by mass (0.29 mol; 100.0 mol% based on the total mol number of polyhydric alcohol)
・ Dodecanedioic acid:
65.5 parts by mass (0.28 mol; 100.0 mol% based on the total mol number of polyvalent carboxylic acid)
The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introduction pipe, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was performed for 3 hours while stirring at a temperature of 140 ° C.
-Tin 2-ethylhexanoate: 0.5 parts by mass After that, the above-mentioned materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C, whereby the crystalline resin D1 was obtained. Was obtained (first reaction step). The obtained crystalline resin D1 had a peak molecular weight Mp10000 and a melting peak temperature of 67 ° C.

<Production Examples of Crystalline Resins D2 and D3>
In the production example of the crystalline resin D1, the monomers and the parts by mass of the polyhydric alcohol component and / or the polycarboxylic acid component in the first reaction step were changed as shown in Table 6, and the crystalline resins D2 and D3 were changed. Obtained. Table 6 shows the physical properties of crystalline resins D2 and D3.

<Production Example of Resin Composition E1>
-Low molecular weight polypropylene (Viscol 660P manufactured by Sanyo Chemical Industries, Ltd.):
51.6 parts by mass (0.11 mol; 15.0 mol% based on the total number of mols of the resin composition monomer)
Xylene: 25.0 parts by mass The above-mentioned material was weighed in a cooling tube, a stirrer, a nitrogen introducing tube, and a reaction vessel equipped with a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased to 175 ° C. while stirring.

·styrene:
30.7 parts by mass (0.29 mol; 42.0 mol% based on the total number of moles of the resin composition monomer)
・ Acrylonitrile:
14.5 parts by mass (0.27 mol; 39.0 mol% based on the total number of moles of the resin composition monomer)
・ Acrylic acid:
0.5 parts by mass (0.01 mol; 1.0 mol% based on the total number of moles of the resin composition monomer)
・ Butyl acrylate:
2.7 parts by mass (0.02 mol; 3.0 mol% with respect to the total mol number of the resin composition monomer)
-Xylene: 10.0 parts by mass-Di-t-butylperoxyhexahydroterephthalate: 0.5 parts by mass After that, the above-mentioned material was added dropwise over 3 hours, and further stirred for 30 minutes. Next, the solvent was distilled off to obtain a resin composition E1. The obtained resin composition E1 had a peak molecular weight Mp6000 and a softening point of 125 ° C.

<Production Example of Toner 1>
30 parts by mass of resin A1 50 parts by mass of resin B1 10 parts by mass of resin C1 10 parts by mass of crystalline resin D1 5 parts by mass of resin composition E1 5 parts by mass of Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C.) Department C. I. Pigment Blue 15:37 parts by mass · 0.3, parts by mass of aluminum 3,5-di-t-butylsalicylate compound (Bontron E88 manufactured by Orient Chemical Industry Co., Ltd.)

Using a Henschel mixer (Model FM-75, manufactured by Nippon Coke Industry Co., Ltd.), the above materials were mixed at a rotation speed of 20 s ^-1 and a rotation time of 5 minutes. -30, manufactured by Ikegai Co., Ltd.). The obtained kneaded material was cooled and coarsely pulverized with a hammer mill to a diameter of 1 mm or less to obtain a coarsely crushed material. The obtained coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Classification was further performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles. Operating conditions, classifying rotor speed of the 130 s ^-1, and the dispersion rotor rotational speed and 120s ^-1.

Using the obtained toner particles, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated toner particles. The operating conditions and the feed amount = 5 kg / hr, and hot-air temperature C = 160 ° C., hot air flow rate = 6 m ³ / min, the cold air temperature E = -5 ° C., the cold air flow rate = 4m ³ / min, the blower air volume = ^{20 m} 3 / And the injection air flow rate = 1 m ³ / min.
To 100 parts by mass of a heat treatment the toner particles obtained, hydrophobic silica (BET: 200m ² /g)1.0 parts by mass of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: a 80m ² / g) 1 0.0 parts by mass were mixed with a Henschel mixer (Model FM-75, manufactured by Nippon Coke Industry Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 minutes to obtain Toner 1. The weight average particle diameter (D4) of Toner 1 was 6.5 μm, and the average circularity was 0.968. Table 7 shows the physical properties of Toner 1.

<Production Examples of Toners 2 to 24>
In the production example of the toner 1, the same operation was performed except that the resin A1, the resin B1, the resin C1, the crystalline resin D1, and the resin composition E1 were changed as shown in Table 7 and the step of the surface treatment apparatus was omitted. Thus, toners 2 to 24 were obtained. Table 7 shows the physical properties of Toners 2 to 24.

<Production Example of Magnetic Core Particle 1>
・ Step 1 (weighing / mixing step):
62.7 parts by mass of Fe ₂ O ₃ 29.5 parts by mass of MnCO ₃ 6.8 parts by mass of Mg (OH) ₂ 1.0 part by mass of SrCO _{3 A} ferrite raw material was weighed so that the above-mentioned material had the above composition ratio. Thereafter, the mixture was pulverized and mixed in a dry vibration mill using 1/8 inch diameter stainless steel beads for 5 hours.

Step 2 (temporary firing step):
The obtained pulverized material was formed into pellets of about 1 mm square with a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh size of 3 mm and then removing the fine powder with a vibrating sieve having a mesh size of 0.5 mm, the pellets were placed in a nitrogen atmosphere (oxygen concentration: 0. (01% by volume) at a temperature of 1000 ° C. for 4 hours to produce a calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

・ Step 3 (crushing step):
After pulverizing to about 0.3 mm with a crusher, using zirconia beads having a diameter of 1/8 inch, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite, and the mixture was pulverized with a wet ball mill for 1 hour. The slurry was pulverized with a wet ball mill using 1/16 inch diameter alumina beads for 4 hours to obtain a ferrite slurry (finely pulverized calcined ferrite).

Step 4 (granulation step):
To a ferrite slurry, 1.0 part by mass of a polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder resin are added to 100 parts by mass of calcined ferrite, and a spray dryer (manufacturer: Okawara Kakoki) And granulated into spherical particles. After adjusting the particle size of the obtained particles, the mixture was heated at a temperature of 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder resin.

Step 5 (firing step):
In order to control the firing atmosphere, the temperature was increased from room temperature to a temperature of 1300 ° C. for 2 hours in a nitrogen atmosphere (oxygen concentration: 1.00% by volume) in an electric furnace, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.

・ Step 6 (sorting step):
After pulverizing the aggregated particles, a low magnetic force product was cut by magnetic separation, and sieved with a sieve having an opening of 250 μm to remove coarse particles. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
8.4% by mass of methyl methacrylate macromonomer
(Macromonomer having a weight average molecular weight of 5,000 having a methacryloyl group at one end)
31.3% by mass of toluene
Methyl ethyl ketone (MEK) 31.3% by mass
Azobisisobutyronitrile 2.0% by mass

Of the above materials, the following materials were added to a four-neck separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a stirrer, and nitrogen gas was introduced to make a sufficient nitrogen atmosphere.
Cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, methyl ethyl ketone.
Thereafter, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours to carry out polymerization. Hexane was poured into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration and dried under vacuum to obtain a coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass of toluene, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content: 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
66.4% by mass of toluene
Carbon black (Regal 330; manufactured by Cabot Corporation) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m2 / g, DBP (dibutyl phthalate) oil absorption 75 mL / 100 g)
The above-mentioned material was dispersed for 1 hour with a paint shaker using zirconia beads having a diameter of 0.5 mm. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of manufacturing magnetic carrier 1>
(Resin coating step):
The coating resin solution 1 was introduced into a vacuum degassing type kneader maintained at room temperature so that 2.5 parts by mass as a resin component was added to 100 parts by mass of the filled core particles 1. After the introduction, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes. After the solvent was volatilized to a certain degree (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier is subjected to magnetic separation to separate low-magnetic-force products, passed through a sieve having an opening of 70 μm, and then classified by an air classifier to obtain a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

<Example of manufacturing two-component developer 1>
8.0 parts by mass of toner 1 was added to 92.0 parts by mass of magnetic carrier 1 and mixed by a V-type mixer (V-20, manufactured by Seishin Enterprise) to obtain two-component developer 1.

<Production Examples of Two-Component Developers 2 to 24>
In the production example of the two-component developer 1, the same operation was performed except for the change as shown in Table 4, and two-component developers 2 to 24 were obtained.

<Example 1>
A two-component developer 1 was charged into a developing device at a cyan position and / or a magenta position using a modified image RUNNER ADVANCE C9075 PRO printer for digital commercial printing manufactured by Canon Inc. as an image forming apparatus. Then, an image in which the amount of applied toner on the paper was desired was formed, and the evaluation described later was performed. The modification points were changed so that the fixing temperature, the process speed, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power could be freely set. In the image output evaluation, an FFh image (solid image) having a desired image ratio was output. FFh is a value in which 256 gradations are displayed in hexadecimal, 00h is the first gradation of 256 gradations (white background), and FFh is 256th gradation of 256 gradations (solid part). .
Evaluation was performed based on the following evaluation methods, and the results are shown in Table 9.

[durability]
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.35 mg / cm ² (FFh image)
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: Chart fixing test environment for A4 paper image ratio 100%: High temperature and high humidity environment: Temperature 30 ° C / relative humidity 85%
Fixing temperature: 170 ° C
Process speed: 450 mm / sec As a durability image output test, 10,000 sheets were output on A4 paper using a band chart of FFh output with an image ratio of 0.1%. Thereafter, the evaluation image was output, and the number of white spots in the image was visually checked.

(Evaluation criteria)
A: Less than 5 white spots (very good)
B: 5 or more and less than 10 white spots (excellent)
C: 10 or more and less than 15 white spots (good)
D: 15 or more and less than 20 white spots (normal)
E: 20 or more white spots (bad)

[Low-temperature fixability]
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 1.20 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 10 cm ² is placed at the center of the A4 paper.
Fixing temperature: 170 ° C
Process speed: 450mm / sec

The evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the image density is measured, and the fixed image is rubbed with the silbon paper (5 reciprocations), and the image density is measured again. Then, the decrease rate of the image density before and after the rubbing was calculated using the following equation. The obtained image density reduction rate was evaluated according to the following evaluation criteria.
Image density reduction rate = (image density after rubbing−image density before rubbing) / image density before rubbing

(Evaluation criteria)
A: Image density reduction rate of less than 2.0% (very excellent)
B: Image density reduction rate 2.0% or more and less than 5.0% (excellent)
C: Image density reduction rate of 5.0% or more and less than 10.0% (good)
D: Image density reduction rate 10.0% or more and less than 15.0% (normal)
E: Image density reduction rate 15.0% or more (poor)

[Hot offset resistance]
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.08 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 10 cm2 was placed on both ends of the A4 paper. Fixing test environment: Normal temperature and low humidity environment: 23 ° C / 5% relative humidity
Fixing temperature: 210 ° C
Process speed: 450mm / sec

The above evaluation image was output, and the hot offset resistance was evaluated. First, after passing ten plain postcards at the center of the fixing belt, the unfixed image was passed. The fog value was used as a hot offset evaluation index. The fog is measured by a reflectometer (“REFLECOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.) and the average reflectance Dr (%) of the evaluation paper before image output (before the fixing test) and the white background after the fixing test are performed. Is measured for the reflectance Ds (%). Then, the fog value was calculated using the following equation. The fog obtained was evaluated according to the following evaluation criteria.
Fog = Dr (%)-Ds (%)

(Evaluation criteria)
A: Fog less than 0.2% (very good)
B: fog 0.2% or more and less than 0.5% (excellent)
C: Fog 0.5% or more and less than 0.8% (good)
D: Fog 0.8% or more, less than 1.0% (normal)
E: fog 1.0% or more (bad)

<Examples 2 to 21 and Comparative Examples 1 to 3>
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 2 to 24 were used. Table 9 shows the evaluation results.
In Example 2, the surface modification step is eliminated, and the compatibility of the crystalline resin is reduced, so that the low-temperature fixing property is inferior to Example 1.
In Example 3, the styrenic resin graft-modified with the aliphatic hydrocarbon compound is eliminated, and the dispersibility of the crystalline resin is reduced.

In Example 4, the difference between the SP value of the resin A and the SP value of the resin B was large, and the mixing property of the resin was reduced, so that the low-temperature fixability and the white spots (durability) were inferior to Example 3.
In Example 5, the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separability was reduced.
In Example 6, the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separation property was reduced. Therefore, the low-temperature fixability and the hot offset resistance were inferior to Example 5.

In Example 7, the molecular weight increases with an increase in the number of moles of the propylene oxide adduct of bisphenol A of resin B, and the plasticization of resin B decreases.
In Example 8, SP (B) increases with the decrease in the number of moles of the propylene oxide adduct of bisphenol A of resin B, and the plasticization of resin B decreases. Is inferior.
Example 9 shows that SP (B) increases and the plasticization of resin B decreases with a decrease in the number of moles of the propylene oxide adduct of bisphenol A added to resin B. Is inferior.

In Examples 10 and 11, the SP value of the resin C was changed (the middle SP value was shifted), and the mixing property between the resin A and the resin B was reduced. Poor offset and white spots (durability).
As described below, “the middle SP value is shifted” means that the SP value of the resin C is almost intermediate between the SP value of the resin A and the SP value of the resin B in the ninth embodiment. In Example 10 or Example 11, it means that the SP value of the resin C approaches the SP value of the resin A or the SP value of the resin B.
Example 9
Difference between SP value of Resin C1 and SP value of Resin B7 = 12.47-12.22 = 0.25
Difference between SP value of resin A4 and SP value of resin C1 = 12.69-12.47 = 0.22
Example 10
Difference between SP value of resin C2 and SP value of resin B7 = 12.52-12.22 = 0.30
Difference between SP value of resin A4 and SP value of resin C2 = 12.69-12.52 = 0.17
Example 11
Difference between SP value of resin C3 and SP value of resin B7 = 12.42-12.22 = 0.20
Difference between SP value of resin A4 and SP value of resin C3 = 12.69-12.42 = 0.27

In Example 12, the resin C2 was changed to the resin C4, the medium SP value was shifted, and the mixing property between the resin A and the resin B was reduced. And white spots (durability) are poor.
Example 12
Difference between SP value of resin C4 and SP value of resin B7 = 12.53-12.22 = 0.31
Difference between SP value of resin A4 and SP value of resin C4 = 12.69-12.53 = 0.16

In Example 13, the resin C3 was changed to the resin C5, the medium SP value was shifted, and the mixing property between the resin A and the resin B was reduced. And white spots (durability) are poor.
Example 13
Difference between SP value of resin C5 and SP value of resin B7 = 12.41-12.22 = 0.19
Difference between SP value of Resin A4 and SP value of Resin C5 = 12.69-12.41 = 0.28

In Example 14, the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separability was lowered. Therefore, the low-temperature fixing property, hot offset resistance, and white spots (durability) ) Is inferior.
In Example 15, the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separability was reduced. Therefore, the low-temperature fixing property, hot offset resistance, and white spots (durability) ) Is inferior.

In Example 16, the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separability was reduced. Therefore, the low-temperature fixability, hot offset resistance, and white spots (durability) ) Is inferior.
In Example 17, since the difference between the SP value of the resin A and the SP value of the resin B was small, and the function separation property was reduced, the low-temperature fixing property, the hot offset resistance, and the white spot (durability) ) Is inferior.

In Example 18, the hot offset resistance and white spots (durability) were inferior to Example 17 because the softening point of the resin A was lowered.
Example 17 Resin A8 Softening point 145 ° C
Example 18 Resin A9 Softening point 130 ° C.

In Example 19, since the softening point of the resin B was high, the low-temperature fixability was inferior to Example 17.
Example 17 Resin B11 Softening point 86 ° C.
Example 19 Resin B13 Softening point 95 ° C

In Example 20, the compatibility between the binder resin and the crystalline polyester is reduced, and therefore, the low-temperature fixability is inferior to Example 17.
Aliphatic diols Example 17 Crystalline Resin D1 hexanediol HO- _{(CH 2)} 6 -OH
Example 20 Crystalline Resin D2 Decanediol HO— (CH ₂ ) ₁₀ —OH
Aliphatic dicarboxylic acid Example 17 Crystalline resin D1 Dodecane diacid HOOC- (CH ₂ ) ₁₀ -COOH
Example 20 Crystalline Resin D2 Sebacic Acid HOOC- (CH ₂ ) ₈ —COOH

In Example 21, the white spots (durability) are inferior to Example 20 because the compatibility between the binder resin and the crystalline polyester is reduced.
In Example 21, as compared with Example 20, the carbon number of the aliphatic diol which is a monomer constituting the crystalline polyester was “more (longer)” and the ester group concentration was “lower” as follows. , "Compatibility decreased".
Aliphatic diols Example 20 Crystalline Resin D2 decanediol HO- _{(CH 2)} 10 -OH
Example 21 Crystalline Resin D3 Dodecanediol HO— (CH ₂ ) ₁₂ —OH

In Comparative Example 1, since there is no resin C, the mixing properties of the resin A and the resin B are very poor, and the low-temperature fixing property, hot offset resistance, and white spots (durability) are extremely inferior to Example 9. .
In Comparative Example 2, the difference between the SP value of the resin A and the SP value of the resin B is small, and plasticization by the crystalline resin acts on both resins. That is, the non-plasticizing plasticizes the amorphous resin which contributes to the improvement of the hot offset resistance, so that the hot offset resistance and the white spots (durability) are extremely inferior to Example 9.
In Comparative Example 3, the difference between the SP value of the resin A and the SP value of the resin B was small, and plasticization by the crystalline resin did not act on either resin. That is, since the amorphous resin which contributes to the improvement of the low-temperature fixability by plasticization is not plasticized, the low-temperature fixability is extremely inferior to Example 9.

101 raw material constant supply means, 102 compressed gas flow rate adjustment means 103 introduction pipe, 104 projecting member 105 supply pipe, 106 processing chamber 107 hot air supply means, 108 cold air supply means 109 regulating means, 110 recovery means 111 hot air supply means outlet, 112 Distributing member 113 Revolving member, 114 Powder particle supply port

Claims (4)

An amorphous resin, a colorant, and a toner having toner particles containing a crystalline resin,
The amorphous resin contains a resin A containing polyester as a main component, a resin B containing polyester as a main component, and a resin C containing polyester as a main component,
The crystalline resin is a resin containing polyester as a main component,
The resin A has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 130 ° C. or more and 150 ° C. or less,
When the compatibility parameter of the resin A obtained by the equation of Fedors was SP (A), the SP (A) is a 12.55 ≦ SP (A) ≦ 13.00 ,
The resin B has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 80 ° C or more and 95 ° C or less,
When the compatibility parameter of the resin B obtained by the formula of Fedors was SP (B), the SP (B) is a 11.80 ≦ SP (B) ≦ 12.40 ,
The resin C has a polyhydric alcohol unit and a polycarboxylic acid unit, and has a softening point of 100 ° C or more and 120 ° C or less,
When the compatibility parameter of the resin C obtained by the equation of Fedors was SP (C), the SP (C) is, the toner, which is a 12.40 ≦ SP (C) ≦ 12.55 . The resin A contains at least 70.0 mol% of a polyhydric alcohol unit derived from an ethylene oxide adduct of bisphenol A, based on the total number of moles of the polyhydric alcohol unit,
The resin B contains 70.0 mol% or more of a polyhydric alcohol unit derived from a propylene oxide adduct of bisphenol A, based on the total number of moles of the polyhydric alcohol unit,
The resin C contains 40.0 mol% or more and 60.0 mol% or less of a polyhydric alcohol unit derived from a propylene oxide adduct of bisphenol A, based on the total number of moles of the polyhydric alcohol unit.
2. The toner according to claim 1, wherein a polyhydric alcohol unit derived from an ethylene oxide adduct of bisphenol A is contained in an amount of 40.0 mol% or more and 60.0 mol% or less based on the total number of moles of the polyhydric alcohol unit.   3. The toner according to claim 1, wherein an average mole number of the propylene oxide adduct of the polyhydric alcohol unit derived from the propylene oxide adduct of bisphenol A of the resin B is 2.5 or more and 3.0 or less. 4. . The toner according to any one of claims 1 to 3, wherein the compatibility parameter SP (A) of the resin A and the compatibility parameter SP (B) of the resin B satisfy the following relationship (Formula 1).
0.65 ≦ SP (A) −SP (B) ≦ 1.00 (Equation 1)

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