JP2023044377A - Toner and two-component developer containing the same - Google Patents

Abstract

To provide a toner which is less likely to cause a burning phenomenon over a long period of time and has excellent hot-offset resistance and low-temperature fixability, and a two-component developer containing the same.SOLUTION: A toner has toner particles containing a resin, a colorant and a release agent, wherein the resin contains an amorphous resin A containing polyester as a main component, an amorphous resin B containing polyester as a main component, an amorphous resin formed of a hybrid resin C having a polyester moiety and a vinyl copolymer moiety, and a crystalline resin D containing polyester as a main component, the amorphous resin A has an SP value of 10.85-11.20(cal/cm3)1/2 and a melting temperature Tm of 90-110°C, the amorphous resin B has an SP value of 10.85-11.20(cal/cm3)1/2 and a melting temperature Tm of 130-150°C, and the hybrid resin C has an SP value of 10.50-10.80(cal/cm3)1/2 and a melting temperature Tm of 125-145°C.SELECTED DRAWING: None

Description

The present invention relates to a toner and a two-component developer containing the same. More particularly, the present invention relates to a toner that is resistant to image sticking over a long period of time and has excellent hot offset resistance and low-temperature fixability, and a two-component developer containing the same.

In recent years, with the remarkable development of OA equipment, electrophotographic apparatuses (image forming apparatuses) such as copiers, printers, and facsimile apparatuses using an electrophotographic method have been widely used.
In addition, the use of contact charging methods using roller charging has increased, and electrophotographic devices such as digital copiers and printers have become longer-lasting, smaller, and faster. I'm in.

Various techniques have been proposed to improve the low-temperature fixability of toner.
For example, in Japanese Patent Laid-Open No. 2017-116807 (Patent Document 1), a toner that can be fixed at a low temperature, has high chroma and brightness, and does not have image defects such as white spots has a specific softening point Tm and a solubility parameter. Amorphous resin A and amorphous resin B having SP values and their specific relative relationships, a resin composition (hybrid) C in which an aliphatic hydrocarbon unit and a vinyl polymerization unit are chemically bonded, A toner is proposed having milled toner particles containing a crystalline polyester resin D, a wax, and a colorant.
In this way, in order to improve the low-temperature fixability of the toner, an incompatible amorphous polyester resin and a compatible polyester resin are used in combination with the crystalline polyester. A proposal has been made to improve the low-temperature fixability by using a compatible amorphous polyester.

JP 2017-116807 A

However, by using a compatible polyester resin having a moderate softening point Tm to form a configuration that facilitates compatibility, the viscosity of the compatible polyester resin portion is greatly reduced when the temperature of the toner becomes high. Due to the uneven distribution of such low-viscosity portions in the toner, the durability of the toner is reduced, causing burning to the magnetic roller during running, and the hot offset resistance during fixing is reduced.
Specifically, in the toner of Patent Document 1, since the softening point Tm of the amorphous resin is low and the SP value is small, it is very compatible with the crystalline polyester. Lack of durability. Further, when the softening point Tm of the resin composition C is between the softening points Tm of the amorphous resins A and B, the viscosity of the resin composition C is significantly reduced when compatible with the crystalline polyester, and durability and Remarkably reduce hot offset resistance.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a toner and a two-component developer containing the same that are resistant to image sticking over a long period of time and have excellent hot offset resistance and low-temperature fixability.

As a result of intensive studies to solve the above problems, the present inventors have found amorphous resin A and amorphous resin B, which are mainly composed of polyester having a specific SP value and melting temperature (softening point) Tm. , a hybrid resin C having a specific SP value and a melting temperature Tm and having a polyester portion and a vinyl copolymer portion, and a resin containing a crystalline resin D mainly composed of polyester, a coloring agent and a releasing agent. The present inventors have completed the present invention based on the discovery that a toner containing toner particles containing the toner containing the toner particles can provide a toner having excellent hot-offset resistance and low-temperature fixability, and a two-component developer containing the same, which is resistant to image sticking over a long period of time. I came to let you.

Thus, according to the present invention, a toner having toner particles comprising a resin, a colorant and a release agent,
The resin is an amorphous resin composed of an amorphous resin A containing polyester as a main component, an amorphous resin B containing polyester as a main component, and a hybrid resin C containing a polyester portion and a vinyl copolymer portion, and Containing a crystalline resin D containing polyester as a main component,
The amorphous resin A has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 90 to 110°C,
The amorphous resin B has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 130 to 150°C,
A toner is provided in which the hybrid resin C has an SP value of 10.50 to 10.80 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 125 to 145°C.

Further, according to the present invention, there is provided a two-component developer containing the above toner and a carrier.

According to the present invention, it is possible to provide a toner and a two-component developer containing the same that are resistant to image sticking over a long period of time and have excellent hot offset resistance and low-temperature fixability.

The present inventor believes that the excellent effects described above are exhibited by the following mechanism.
Amorphous resin (hereinafter also referred to as "resin C") composed of hybrid resin C having a polyester moiety and a vinyl copolymer moiety is amorphous resin A (hereinafter also referred to as "resin A") containing polyester as a main component. ) and polyester-based amorphous resin B (hereinafter also referred to as “resin B”), it has the property of maintaining a high viscosity in a high temperature range, so a hybrid having a high melting temperature Tm can be added. can suppress excessive reduction in viscosity in a high-temperature region, and can maintain high kneading strength during melt-kneading. In addition, since the SP value of resin C is closer to crystalline resin D (hereinafter also referred to as "resin D") containing polyester as a main component than resins A and B, relatively incompatible resins A and B can be used together. Even in this case, the resin D in the toner can be highly finely dispersed. The finer the dispersion of the resin D, the more it is possible to suppress the exposure to the toner surface, so the durability is improved, it is possible to suppress the sticking to the magnetic roller during running, and the hot offset resistance is improved. .
Further, by making the SP value of resin C closer to that of resin D than resins A and B, a state in which resin C surrounds resin D can be created. As a result, the exposure of the resin D to the toner surface can be further suppressed, and the highly finely dispersed resin D quickly reduces the viscosity of the surrounding resin during fixing heating, thereby improving the low-temperature fixability. Even in a region where the fixing temperature is high, resin C maintains a relatively high viscosity, and relatively incompatible resins A and B are present in the toner at a sufficient ratio. Since the viscosity can be suppressed, hot offset resistance is improved.

(A) Toner The toner of the present invention is a toner having toner particles containing a resin, a colorant and a release agent,
The resin is an amorphous resin composed of an amorphous resin A containing polyester as a main component, an amorphous resin B containing polyester as a main component, and a hybrid resin C containing a polyester portion and a vinyl copolymer portion, and Containing a crystalline resin D containing polyester as a main component,
The amorphous resin A has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 90 to 110°C,
The amorphous resin B has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 130 to 150°C,
The hybrid resin C is characterized by having an SP value of 10.50 to 10.80 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 125 to 145°C.
Hereinafter, the resin and release agent which are characteristic parts of the toner of the present invention will be described, and the toner, other basic configurations, and the two-component developer containing the toner will be described.

(1) Resin The resin constituting the toner of the present invention is a combination of at least four resins having specific SP values and melting temperatures Tm.

(1-1) Physical Properties of Amorphous Resin A (Resin A) Resin A is mainly composed of polyester and has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and 90 to 110°C. has a melting temperature Tm of
When the SP value is less than 10.85 (cal/cm ³ ) ^1/2 , it becomes more compatible with resin D, and durability may decrease. On the other hand, when the SP value exceeds 11.20 (cal/cm ³ ) ^1/2 , it becomes difficult to be compatible with resin D, the kneading state in toner preparation deteriorates, poor dispersion of resin D occurs, and low-temperature fixation occurs. sexuality may worsen.
A preferable SP value of Resin A is 10.95 to 11.10 (cal/cm ³ ) ^1/2 .
On the other hand, if the melting temperature Tm is less than 90° C., the viscosity of the toner may decrease and the durability and hot offset resistance may deteriorate. On the other hand, when the melting temperature Tm exceeds 110° C., the viscosity of the toner increases, and the low-temperature fixability may deteriorate.
A preferable melting temperature Tm of the resin A is 95 to 105°C.

(1-2) Physical Properties of Amorphous Resin B (Resin B) Resin B is mainly composed of polyester and has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and 130 to 150°C. has a melting temperature Tm of
When the SP value is less than 10.85 (cal/cm ³ ) ^1/2 , it becomes more compatible with resin D, and durability may decrease. On the other hand, when the SP value exceeds 11.20 (cal/cm ³ ) ^1/2 , it becomes difficult to be compatible with resin D, the kneading state in toner preparation deteriorates, poor dispersion of resin D occurs, and low-temperature fixation occurs. sexuality may worsen.
A preferable SP value of Resin B is 10.95 to 11.10 (cal/cm ³ ) ^1/2 .
On the other hand, if the melting temperature Tm is less than 130° C., the viscosity of the toner may decrease and the durability and hot offset resistance may deteriorate. On the other hand, when the melting temperature Tm exceeds 150° C., the viscosity of the toner increases, and low-temperature fixability may deteriorate.
A preferable melting temperature Tm of the resin B is 135 to 145°C.

(1-3) Physical Properties of Hybrid Resin C (Resin C) Resin C has a polyester portion and a vinyl copolymer portion, and has an SP value of 10.50 to 10.80 (cal/cm ³ ) ^1/2 . and a melting temperature Tm of 125-145°C.
When the SP value is less than 10.50 (cal/cm ³ ) ^1/2 , it becomes more compatible with Resin D, and durability may decrease. On the other hand, when the SP value exceeds 10.80 (cal/cm ³ ) ^1/2 , it becomes difficult to be compatible with resin D, the kneading state in toner preparation deteriorates, resin D is poorly dispersed, and low-temperature fixation occurs. sexuality may worsen.
A preferable SP value of Resin C is 10.55 to 10.75 (cal/cm ³ ) ^1/2 .
On the other hand, if the melting temperature Tm is less than 125° C., the viscosity of the toner may decrease and the durability and hot offset resistance may deteriorate. On the other hand, when the melting temperature Tm exceeds 145° C., the viscosity of the toner increases, and low-temperature fixability may deteriorate.
A preferable melting temperature Tm of the resin C is 130 to 140°C.

(1-4) Physical Properties of Crystalline Resin D (Resin D) Resin D is mainly composed of polyester.
Resin D preferably has an SP value of 9.40-9.60 (cal/cm ³ ) ^1/2 .
By setting the SP value of the resin D within the above range, the compatible state of the resins A to C and the resin D becomes more optimal, and the durability of the toner can be enhanced while maintaining high low-temperature fixability.
When the SP value is less than 9.40 (cal/cm ³ ) ^1/2 , the compatibility with Resins A to C is less likely to deteriorate (compatibility becomes easier), so the kneading state deteriorates and Resin D is dispersed. Defects may occur and the low-temperature fixability may deteriorate. On the other hand, when the SP value exceeds 9.60 (cal/cm ³ ) ^1/2 , it tends to be compatible with the amorphous polyester, and the durability may decrease.
A more preferable SP value of Resin D is 9.45 to 9.55 (cal/cm ³ ) ^1/2 .

(1-5) Materials for resins A, B and D Resins A, B and D are polyester-based resins containing polyester as the main component, Resins A and B are amorphous, Resin D is crystalline, As long as it has the above-mentioned specific physical properties, a polyester resin commonly used in the art can be used, and a commercially available product can be used by appropriately polymerizing a monomer.
The polyester resin is usually one or more selected from dihydric alcohol components and trihydric or higher polyhydric alcohol components, and one or more selected from divalent carboxylic acids and trihydric or higher polycarboxylic acids. can be obtained by polycondensation, esterification, or transesterification by a known method.
The conditions for the polycondensation reaction may be appropriately set according to the reactivity of the monomer components, and the reaction may be terminated when the polymer has suitable physical properties. For example, the reaction temperature is about 170 to 250° C., and the reaction pressure is about 5 mmHg to normal pressure.

(1-5-1) Resins A and B (amorphous polyester resin)
The amorphous polyester resin is not particularly limited, but can be obtained, for example, by a polycondensation reaction between a carboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a polyhydric alcohol containing ethylene glycol as a main component.
The reaction conditions are the same as in the production of ordinary polyester resins. For example, a dicarboxylic acid monomer and a polyhydric alcohol are mixed in a nitrogen gas atmosphere, if necessary, in the presence of an esterification catalyst at a temperature of 190 to 240°C. By reacting with, an amorphous polyester resin is obtained. The reaction ratio between the polyhydric alcohol and the carboxylic acid monomer is preferably from 1.3:1 to 1:1.2 in terms of the equivalent ratio [OH]:[COOH] between the hydroxyl group and the carboxyl group.

The molar content of terephthalic acid or isophthalic acid in the dicarboxylic acid monomer is preferably 70-100%, more preferably 80-100%.
Dicarboxylic acid monomers may also include aromatic dicarboxylic acids such as fumaric acid, aliphatic dicarboxylic acids such as adipic acid, sebacic acid and succinic acid, ester-forming derivatives of terephthalic acid or isophthalic acid, aromatic Ester-forming derivatives of dicarboxylic acids, ester-forming derivatives of aliphatic dicarboxylic acids, acid anhydrides and alkyl esters of these carboxylic acids may also be included.
Furthermore, the dicarboxylic acid monomer may be used in combination with a trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid, or an ester-forming derivative thereof.
The above dicarboxylic acid monomers and polycarboxylic acid monomers may be used alone or in combination of two or more.

The molar content of ethylene glycol in the polyhydric alcohol is preferably 70-100%, more preferably 80-100%.
Polyhydric alcohols may include other polyhydric alcohols such as 1,3-propylene glycol and 1,4-butanediol.
The above polyhydric alcohols may be used singly or in combination of two or more.

(1-5-2) Resin D (crystalline polyester resin)
The crystalline polyester-based resin is not particularly limited. It is preferably composed of linear saturated aliphatic polyester units obtained by polycondensation reaction with alcohol.
The reaction conditions are the same as in the production of ordinary polyester resins. For example, a dicarboxylic acid monomer and a polyhydric alcohol are mixed in a nitrogen gas atmosphere, if necessary, in the presence of an esterification catalyst at a temperature of 190 to 240°C. By reacting with, a crystalline polyester resin is obtained. The reaction ratio between the polyhydric alcohol and the carboxylic acid monomer is preferably 0.83:1 to 1.3:1 in terms of the equivalent ratio [OH]:[COOH] between the hydroxyl group and the carboxyl group from the viewpoint of toner storage stability. is.

The molar content of the dicarboxylic acid in the carboxylic acid monomer is preferably 90 to 100%. If the molar content of the dicarboxylic acid is low, the rate and speed of crystallization decrease, resulting in insufficient toner aggregation resistance. can be
Examples of aliphatic dicarboxylic acids having 9 to 22 carbon atoms include azelaic acid, zebacic acid, 1,10-decanedicarboxylic acid and 1,18-octadecanedicarboxylic acid. Carboxylic acid monomers and polycarboxylic acid monomers may also contain ester-forming derivatives of these aliphatic dicarboxylic acids.
Furthermore, the carboxylic acid monomer may be used in combination with a trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid, or an ester-forming derivative thereof.
The above carboxylic acid monomers may be used singly or in combination of two or more.

The molar content of the aliphatic diol having 2 to 10 carbon atoms in the polyhydric alcohol is preferably 80 to 100%.
Examples of aliphatic diols having 2 to 10 carbon atoms include ethylene glycol, 1,4-butanediol and 1,6-hexanediol.
Polyhydric alcohols that can be used in combination with the aliphatic diols include trihydric or higher alcohols such as glycerin and trimethylolpropane.
The above polyhydric alcohols may be used singly or in combination of two or more.

(1-5-3) Amorphous resin and crystalline resin In the present invention, the amorphous resin and the crystalline resin are distinguished by the crystallinity index, and the crystallinity index is in the range of 0.6 to 1.5. A resin is defined as a crystalline resin, and a resin having a crystallinity index of less than 0.6 or greater than 1.5 is defined as an amorphous resin. That is, resins with a crystallinity index of more than 1.5 are amorphous, while resins with a crystallinity index of less than 0.6 have low crystallinity and a large amount of amorphous parts.
The crystallinity index is a physical property that serves as an index of the degree of crystallization of a resin, and is defined by the ratio of the softening temperature to the maximum endothermic peak temperature (softening temperature/maximum endothermic peak temperature). Here, the maximum endothermic peak temperature refers to the temperature of the highest endothermic peak among the observed endothermic peaks. In the crystalline polyester resin, the maximum peak temperature is defined as the melting point Tmp, and in the non-crystalline polyester resin, the peak on the highest temperature side is defined as the glass transition temperature Tg.
The degree of crystallization can be controlled by adjusting the type and ratio of raw material monomers, production conditions (eg, reaction temperature, reaction time, cooling rate), and the like.

The weight average molecular weights of resins A, B and D have little effect on the effect of the present invention and are not particularly limited, but resin A is about 2000 to 20000, resin B is about 100000 to 10000000, and resin D is about 3000 to 50000. degree.
Resins A, B and D specifically include resins A1 to A5, resins B1 to B5 and resins D1 to D5 produced in Examples, respectively.

(1-6) Material of Resin C Resin C is an amorphous resin composed of a hybrid resin C having a polyester portion and a vinyl copolymer portion, in other words, a composite resin of a polyester resin and a vinyl resin. .
Resin C is obtained by, for example, a step of polycondensing an alcohol component and a carboxylic acid component [referred to as "a raw material monomer for amorphous polyester resin" in the examples] to obtain a polyester resin. It can be obtained by a method including a step of addition polymerization in the presence of a polymerization initiator such as peroxide to obtain a vinyl resin.
For example, a polycondensation reaction between an alcohol component containing a dihydric or higher alcohol and, for example, a carboxylic acid component containing a dihydric or higher carboxylic acid compound is carried out in an inert gas atmosphere, if necessary, gallic It can be carried out in the presence of an esterification co-catalyst such as an acid, a polymerization inhibitor, or the like.
A polyester resin containing 3 to 18 mol of an aromatic carboxylic acid compound having a valence of 3 or more and a raw material containing 25 to 50% by mass or less of a (meth)acrylic acid alkyl ester with respect to 100 mol of an alcohol component as a carboxylic acid component. It is a composite resin with a vinyl resin that is an addition polymer of a monomer.

Examples of alcohol components include alkylene oxide adducts of bisphenol A, such as mixtures of ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A, ethylene glycol, 1,2-propanediol and 1,3-propanediol. , 1,4-butanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, and trihydric or higher alcohols such as sorbitol, pentaerythritol, glycerin, and trimethylolpropane.

The carboxylic acid component preferably contains a trivalent or higher aromatic carboxylic acid and a divalent carboxylic acid (dicarboxylic acid).
Aromatic dicarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid; anhydrides of these acids and alkyl esters of these acids.
Aliphatic dicarboxylic acids include succinic acid, fumaric acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, succinic acid having an alkyl group or alkenyl group in the side chain, these acid anhydrides.

Raw material monomers for the vinyl resin preferably contain (meth)acrylic acid [indicated as “bi-reactive monomer” in the examples], (meth)acrylic acid alkyl ester, and further styrene or a styrene derivative.
Examples of (meth)acrylic acid alkyl esters [indicated as “raw material monomers for styrene-based resins” in the examples] include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, 2- Hydroxyethyl (meth)acrylate, (iso- or tertiary) butyl (meth)acrylate.
As used herein, "(meth)acryl" means "methacryl" or "acryl."
Styrene and styrene derivatives include, for example, styrene, α-methylstyrene, vinyltoluene and derivatives thereof.
Raw material monomers for other vinyl resins include, for example, ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate. vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone.

Resin C is, for example, an amorphous composite resin described in Japanese Patent No. 6675263 and an amorphous polycondensation resin component and an addition polymerization resin component described in Japanese Patent Application Laid-Open No. 2013-109237. Examples include hybrid resins, specifically, resins C1 to C5 produced in Examples.
The weight-average molecular weight of Resin C has little effect on the effects of the present invention, and is not particularly limited, but is about 100,000 to 1,000,000.

(1-7) Blending Ratio of Resin The blending ratio of the resin in the toner base particles may be appropriately set so as to obtain the desired effect of the present invention.
For example, the mixing ratios of resin A, resin B, resin C and resin D in the toner base particles are 20 to 50% by mass, 20 to 60% by mass, 5 to 25% by mass and 1 to 15% by mass, respectively.

The mass ratio B/C between resin B and resin C is preferably 1.5 to 6.0.
By setting the ratio of the resin B and the resin C within the above range, the dispersibility of the resin D can be further improved, and excessive viscosity reduction in the high temperature range can be prevented, and the toner can be produced while maintaining high low-temperature fixability. durability can be increased.
If the mass ratio B/C is less than 1.5, the proportion of resin C increases and the portion that is easily compatible with resin D becomes relatively large, resulting in reduced durability at high temperatures and reduced hot offset resistance. Sometimes. On the other hand, when the mass ratio B/C exceeds 6.0, the ratio of resin C becomes low, and the portion easily compatible with resin D becomes relatively small, so the toner melting speed during fixing slows down, and low-temperature fixing occurs. sexuality may worsen.
A more preferable mass ratio B/C is 2.0 to 4.5.
For example, the total amount of resin B and resin C in the toner base particles is 1.0 to 2.4 with respect to 1 mass of resin A.

The mass ratio C/D between resin C and resin D is preferably 1.0 to 5.0.
By setting the addition amount of the resin C, which is highly compatible with the resin D, within the above range, the dispersed state of the resin D in the toner is improved, and the effect of plasticizing the amorphous resin by the resin D is maximized. Therefore, low-temperature fixability is improved.
If the mass ratio C/D is less than 1.0, the dispersibility of the resin D may deteriorate, and the toner durability and hot offset resistance may deteriorate. On the other hand, when the mass ratio C/D exceeds 5.0, the plasticizing effect of the resin D on the resin C is weakened, so that the low-temperature fixability may deteriorate.
A more preferable mass ratio C/D is 1.5 to 4.0.
For example, the total amount of resin C and resin D in the toner base particles is 0.3 to 0.8 with respect to 1 mass of resin A.

(2) Release Agent As the release agent contained in the toner of the present invention, a release agent commonly used in the art can be used.
For example, petroleum-based waxes such as paraffin wax and microcrystalline wax and derivatives thereof; Fischer-Tropsch wax, polyolefin waxes (polyethylene wax, polypropylene wax, etc.), low molecular weight polypropylene waxes and polyolefin polymer waxes (low molecular weight polyethylene wax, etc.) ) and derivatives thereof; vegetable waxes such as carnauba wax, rice wax and candelilla wax and their derivatives; animal waxes such as beeswax, spermaceti; fatty acid amides and phenolic fatty acid esters. long-chain carboxylic acids and their derivatives; long-chain alcohols and their derivatives; silicone-based polymers; higher fatty acids and the like.
The above derivatives include oxides, block copolymers of vinyl-based monomers and wax, and graft-modified products of vinyl-based monomers and wax.
In the present invention, one of the release agents described above may be used alone, or two or more thereof may be used in combination.

Among the release agents described above, the release agent is preferably an ester wax obtained from a long-chain carboxylic acid and an alcohol. Examples of the ester waxes include ester waxes described in Japanese Patent No. 4435434 and Japanese Patent No. 6545538, and specifically, waxes used in Examples.
By using an ester wax that is well compatible with the resin D as the release agent, the degree of crystallinity of the resin D and the ester wax after melt-kneading is higher than when the resin D and the ester wax are used alone, thereby improving the durability of the toner.

Moreover, the ester wax is preferably a wax having an ester component with a linear molecular structure.
By making the molecular structure of the ester wax linear, the degree of crystallinity of the resin D and the ester wax, which also have a linear structure, is higher than when they are used alone, thereby lowering the viscosity of the toner when not heated. can be suppressed, and the durability of the toner is improved.

The content of the release agent in the toner of the present invention is not particularly limited, but is preferably 1 to 10% by mass.
When the content of the release agent is within the above range, an image having a high image density and very good image quality can be formed without impairing various physical properties of the toner.

(3) Colorant As the colorant contained in the toner of the present invention, various types and colors of organic and inorganic pigments and dyes commonly used in the art can be used, for example, black and white. , yellow, orange, red, purple, blue and green colorants.

Examples of black colorants include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, non-magnetic ferrite, magnetic ferrite and magnetite. Examples of white colorants include zinc oxide, titanium oxide, antimony white, zinc sulfide and the like.

Examples of yellow coloring agents include yellow lead, zinc yellow, cadmium yellow, iron oxide yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine. Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 138 and the like.

Examples of orange colorants include red chrome, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indanthrene brilliant orange RK, benzidine orange G, indanthrene brilliant orange GK, C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43 and the like.

Examples of red colorants include red iron oxide, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resole red, pyrazolone red, watching red, calcium salts, lake red C, lake red D, and brilliant carmine 6B. , eosin lake, rhodamine lake B, alizarin lake, brilliant carmine 3B, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48:1, C.I. I. Pigment Red 53:1, C.I. I. Pigment Red 57:1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment Red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.

Examples of purple colorants include manganese purple, fast violet B, and methyl violet lake.
Blue colorants include, for example, Prussian Blue, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-Free Phthalocyanine Blue, Partially Chlorinated Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:2, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60 and the like.
Examples of green colorants include chrome green, chromium oxide, picment green B, micalite green lake, final yellow green G, C.I. I. Pigment Green 7 and the like.

In the toner of the present invention, one of the above colorants may be used alone or two may be used in combination, and the combination may be of different colors or of the same color.
Moreover, two or more kinds of colorants may be formed into composite particles and used. Composite particles can be produced, for example, by adding an appropriate amount of water, a lower alcohol, or the like to two or more colorants, granulating the mixture with a general granulator such as a high-speed mill, and drying. Furthermore, in order to uniformly disperse the colorant in the resin, it may be used in the form of a masterbatch. The composite particles and masterbatch are incorporated into the toner composition during dry mixing.

The content of the colorant in the toner of the present invention is not particularly limited, but is preferably 1 to 10% by mass.
When the content of the colorant is within the above range, an image having a high image density and very good image quality can be formed without impairing various physical properties of the toner.

(4) Charge Control Agent The toner base particles of the present invention may contain a charge control agent, but preferably do not contain a charge control agent in order to suppress an increase in charge amount.
As the charge control agent, a charge control agent for negative charge control commonly used in the art can be used.
Examples of charge control agents for negative charge control include oil-soluble dyes such as oil black and spirone black, metal-containing azo compounds, azo complex dyes, metal naphthenate salts, metal complexes and metal salts of salicylic acid and its derivatives ( metals include chromium, zinc, zirconium, etc.), boron compounds, fatty acid soaps, long-chain alkyl carboxylates, resin acid soaps, and the like.
In the toner of the present invention, one of the above charge control agents can be used alone or two or more of them can be used in combination.

The content of the charge control agent in the toner of the present invention is not particularly limited, but is preferably 0.1 to 5 mass %.
If the content of the charge control agent is within the above range, an image having a high image density and excellent image quality can be formed without impairing various physical properties of the toner.

(5) Toner Particles The toner base particles contained in the toner of the present invention contain at least a resin, a colorant and a release agent, and if necessary, known additives within a range that does not impair the effects of the present invention. You can stay.
The toner of the present invention is used as a one-component developer in which the toner base particles further contain an external additive, or a two-component developer in which the external additive is further contained and mixed with a carrier.
Note that the toner before adding the external additive is also referred to as “toner base particles”.
External additives generally have the function of improving the transportability and chargeability of the toner, and the agitation of the toner with the carrier when the toner is made into a two-component developer.

As the external additive, an external additive commonly used in the relevant technical field can be used. Examples thereof include silica, titanium oxide, etc., and are surface-treated (hydrophobicized) with a silicone resin, a silane coupling agent, or the like. It is preferable to have
Although the average primary particle size of the external additive is not particularly limited, it is preferably 1 to 200 nm.
The amount of the external additive compounded is not particularly limited, but is preferably 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, relative to 100 parts by weight of the toner base particles.

(6) Method for producing toner The toner base particles used in the present invention are produced by a known method using a known apparatus commonly used in the art, for example, by coarsely pulverizing at least a resin, a colorant and a release agent. A mixing step of mixing the melt-kneaded product and the filler, a finely pulverizing step of finely pulverizing the mixture obtained in the mixing step, a classification step of classifying the finely pulverized product obtained in the finely pulverizing step, It can be manufactured by a spheronization treatment step of spheroidizing the classified material obtained in the classification step with hot air.
The dry method is preferred in that it requires fewer steps than the wet method and does not require equipment costs, and the pulverization method is particularly preferred.
The conditions in each step may be appropriately set depending on the target material and desired physical properties.

For mixing, known devices commonly used in the technical field, for example, Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd. (now Nippon Coke Industry Co., Ltd.)), super mixer (trade name, manufactured by Kawata Co., Ltd.), Henschel type mixing device such as Mechanomill (trade name, manufactured by Okada Seiko Co., Ltd.), Ong Mill (trade name, manufactured by Hosokawa Micron Corporation), Hybridization System (trade name, manufactured by Nara Machinery Co., Ltd.), Cosmo System (trade name) , manufactured by Kawasaki Heavy Industries, Ltd.) can be used.
Melt-kneading includes known devices commonly used in the art, such as general kneaders such as a twin-screw extruder, a three-roll roll, and a lab blast mill. Specifically, for example, TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65/87, PCM-30 (all of these are trade names, manufactured by Ikegai Co., Ltd.). An open roll kneader such as Extruder or Kneedex (trade name, manufactured by Mitsui Mining Co., Ltd.) can be used.
For fine pulverization, known devices that are commonly used in the art, such as a jet pulverizer that pulverizes using a supersonic jet stream, a rotor that rotates at high speed and a stator (liner) An impact pulverizer can be used that introduces and pulverizes the solidified material into the space formed between them.
Classification can be performed using a known device commonly used in the art, for example, a classifier capable of removing excessively pulverized toner particles by centrifugal force and wind power, such as a swirling air classifier (rotary air classifier).

The toner of the present invention is produced by a first external addition step of externally adding externally added silica to toner base particles by a known method using a known apparatus commonly used in the art, and further externally adding externally added fine particles. It can be produced by the second external addition step.
The conditions in each step may be appropriately set depending on the target material and desired physical properties.

(B) Two-component developer The two-component developer of the invention contains the toner of the invention and a carrier.
The toner of the present invention can be used either in the form of a one-component developer or a two-component developer. When used as a two-component developer, a carrier is further blended in addition to the external additive.
As the carrier, carriers commonly used in the art can be used. For example, single or composite ferrite and carrier core particles made of iron, copper, zinc, nickel, cobalt, manganese, chromium, etc. are coated with a known coating substance. The surface-coated one etc. are mentioned.
The average particle size of the carrier is preferably 10-100 μm, more preferably 20-50 μm.
Although the blending amount of the toner and the carrier is not particularly limited, the content of the external additive toner in the two-component developer is preferably 3 to 12% by mass.

EXAMPLES The present invention will be specifically described below with reference to production examples, working examples, and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
In Examples and Comparative Examples, each physical property value was measured by the method shown below.

[Resin solubility parameter SP value: (cal/cm ³ ) ^1/2 ]
ROBERT F., proposed by Fedors et al. FEDORS, " ^POLYMER ENGINEERING AND SCIENCE", February 1994, Vol. 14, No. 2, p ^. Calculate

[Resin melting temperature Tm: ° C.]
Using a flow property evaluation device (flow tester, manufactured by Shimadzu Corporation, model: CFT-100C), a load of 20 kgf/cm ² (9.8 × 10 ⁵ Pa) was applied, and the sample was allowed to flow out from a die (nozzle diameter 1 mm, length 1 mm). The temperature at which half of the sample flows out is defined as the melting temperature Tm (°C) of the resin.

[Volume average particle diameter of toner base particles: μm]
20 mg of the sample and 1 ml of sodium alkyl ether sulfate were added to 50 ml of the electrolytic solution (manufactured by Beckman Coulter, Inc., trade name: ISOTON-II), and an ultrasonic disperser (manufactured by AS ONE Corporation, a desktop dual-frequency ultrasonic cleaner) was added. , Model: VS-D100) is used for dispersion treatment at a frequency of 20 kHz for 3 minutes to obtain a sample for measurement. The obtained measurement sample was measured using a particle size distribution analyzer (manufactured by Beckman Coulter, Inc., model: Multisizer4e) under the conditions of an aperture diameter of 100 μm and the number of particles to be measured: 50000 counts. A volume average particle diameter (μm) is obtained from the particle size distribution.

(Production Examples 1 to 5 and Comparative Production Examples 1 to 4: Preparation of amorphous polyester A)
100 parts by mass of the raw material monomer of the polyester resin in the molar part ratio shown in Table 1, 0.5 parts by mass of tin (II) 2-ethylhexanoate as an esterification catalyst, and gallic acid (3,4) as an esterification co-catalyst ,5-trihydroxybenzoic acid) is placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and heated in a nitrogen atmosphere with a mantle heater. The temperature was raised to 210° C. over 5 hours. After that, reaction was carried out at a pressure of 8.0 kPa until the melting temperature Tm shown in Table 1 was reached, and amorphous polyester resins A1 to A9 were obtained.
The melting temperature of the obtained resin was measured, and the obtained physical property values are shown in Table 1 together with the resin raw materials and their usage ratios.

(Production Examples 6-10 and Comparative Production Examples 5-8: Preparation of amorphous polyester B)
100 parts by mass of the raw material monomer for the amorphous polyester resin other than trimellitic anhydride in the mole part ratio shown in Table 2, 0.5 parts by mass of tin (II) 2-ethylhexanoate as an esterification catalyst, and an esterification assistant 0.05 part by mass of gallic acid as a catalyst was placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and heated to 235 in a nitrogen atmosphere in a mantle heater. C. over 3 hours, and after reaching a temperature of 235.degree. C., the temperature was maintained for 7 hours. Then, after cooling to a temperature of 210° C., trimellitic anhydride was added, the temperature was maintained at 210° C. for 1 hour, and the reaction was performed under reduced pressure at a pressure of 8.0 kPa. was performed to obtain amorphous polyester resins B1 to B9.
The melting temperature of the obtained resin was measured, and the obtained physical property values are shown in Table 2 together with the resin raw materials and their usage ratios.

(Production Examples 11-15 and Comparative Production Examples 9-12: Preparation of hybrid resin C)
A 10-liter four-neck flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen inlet tube was charged with raw material monomers for a polyester resin other than trimellitic anhydride at the molar ratio shown in Table 3. The temperature was raised to 160° C. in a mantle heater in a nitrogen atmosphere. A mixture of a raw material monomer for a styrene resin, a bi-reactive monomer, and dibutyl peroxide as a polymerization initiator was added dropwise thereto to carry out polymerization. Thereafter, 0.5 parts by mass of tin (II) 2-ethylhexanoate as an esterification catalyst and 0.05 parts by mass of gallic acid as an esterification co-catalyst were added to 100 parts by mass of the above monomer, and the temperature was raised to 210°C for 5 minutes. The temperature was raised over time. After that, trimellitic anhydride was added, the temperature was raised to 220° C., and the reaction was carried out at a pressure of 8.0 kPa until the melting temperature Tm shown in Table 3 was reached, to obtain hybrid resins C1 to C9.
The melting temperature of the obtained resin was measured, and the obtained physical property values are shown in Table 3 together with the resin raw materials and their usage ratios.

(Production Examples 16 to 20: Preparation of crystalline polyester resin D)
Equipped with 100 parts by mass of the monomer component in the mole part ratio shown in Table 4, 0.2 parts by mass of tin (II) 2-ethylhexanoate as an esterification catalyst, a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple. It is placed in a four-necked flask with a capacity of 10 liters, heated from 130 ° C. to 200 ° C. over 10 hours under a nitrogen atmosphere, and reacted at a temperature of 200 ° C. and a pressure of 8.0 kPa for 1 hour to crystallize. to obtain flexible polyester resins D1 to D5.
Table 4 shows the solubility parameter SP value of the obtained resin together with the resin raw materials and their usage ratios.

(Production Example 21: Preparation of release agent W1)
1.5 mol of stearic acid as an acid component and 1.5 mol of stearyl alcohol as an alcohol component were charged into a 2-liter four-necked flask equipped with a stirrer, a thermocouple and a nitrogen inlet tube. An esterification reaction was carried out at a temperature of 220° C. under a nitrogen stream to obtain a reactant.
After that, 26 parts by mass of a mixed solvent of toluene and ethanol (mixing mass ratio: 20:6) was added to the flask with respect to 100 parts by mass of the esterification reaction product to dissolve the obtained reaction product. Furthermore, 10 parts by mass of sodium hydroxide aqueous solution with a concentration of 10% by mass was added to the flask and stirred at a temperature of 70° C. for 30 minutes. The flask was allowed to stand for 30 minutes, the contents of the flask were separated into organic and aqueous layers, and the aqueous layer was removed from the contents.
After that, add 20 parts by mass of ion-exchanged water to the flask, stir at a temperature of 70° C. for 30 minutes, then allow the flask to stand still for 30 minutes, separate the contents in the flask into an aqueous layer and an organic layer, and The aqueous layer was removed from the mass and this operation was repeated 5 times. The solvent was distilled off from the organic layer of the content in the obtained flask under reduced pressure conditions to obtain an ester wax W1 having a linear structure.

(Production Example 22: Preparation of release agent W2)
Instead of preparing a wax, a commercially available linear paraffin wax (manufactured by Nippon Seiro Co., Ltd., product name: HNP-10PD, W2) was used.

(Production Example 23: Preparation of release agent W3)
Using 3 mol of stearic acid as an acid component and 0.75 mol of pentaerythritol as an alcohol component, according to Production Example 21, an ester wax W3 having a stereostructure was obtained.

(Example 1: Preparation of toner)
[Material mixing, kneading, crushing, and classifying process]
Toner base particles used in Examples and Comparative Examples were prepared as follows.
Amorphous resin A: Resin A-1 (Production Example 1) 30% by mass
Amorphous resin B: Resin B-1 (Production Example 6) 40% by mass
Amorphous resin made of hybrid resin C: Resin C-1 (Production Example 11) 14% by mass
Crystalline resin D: Resin D-1 (Production Example 16) 8% by mass
Colorant: Colorant (CIPigment Blue 15:3, manufactured by DIC Corporation) 4% by mass
Release agent: Wax W1 (Production Example 21) 3% by mass
Charge control agent: salicylic acid compound (Orient Chemical Industry Co., Ltd., trade name: Bontro E84) 1% by mass

After pre-mixing and dispersing the above materials for 5 minutes using an airflow mixer (Henschel Mixer, manufactured by Mitsui Mining Co., Ltd. (currently Nippon Coke Industry Co., Ltd.), model: FM20C), a twin-screw extruder (Ikegai Co., Ltd. PCM-30) was used to obtain a kneaded product by melt-kneading under the conditions of a set cylinder temperature of 110° C., a barrel rotation speed of 300 rpm, and a raw material feed rate of 20 kg/hour.
After cooling the obtained kneaded product with a cooling belt, it was coarsely pulverized using a cutting mill (manufactured by Dalton, model: D-200) to obtain a coarsely pulverized product.
The resulting coarsely crushed product was pulverized with a jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd., model: IDS-2) to obtain a finely pulverized product.
The obtained finely pulverized product was classified by an elbow jet classifier (manufactured by Nittetsu Mining Co., Ltd., model: EJ-LABO) to obtain non-externally added toner base particles.

[External addition process]
To 100 parts by mass of the resulting toner base particles, 1.0 part by mass of a first external additive (hydrophobic fumed silica, average primary particle size: 12 nm, manufactured by Aerosil, trade name: R974) and a third 2 Add 1.5 parts by mass of an external additive (colloidal silica, average primary particle size 115 nm, manufactured by Cabot Corporation, trade name: TG-C191) and stir with the above airflow mixer to obtain a volume average particle size of 6.5 μm. of externally added toner base particles were obtained.

[Preparation of developer]
The obtained externally added toner base particles and coat carrier (manufactured by Sharp Corporation, name: genuine carrier for MX-5111FN) were mixed with a V-type mixer (manufactured by Tokuju Kosakusho Co., Ltd., product name: V-5) and mixed for 20 minutes to obtain a two-component developer.

(Examples 2 to 27 and Comparative Examples 1 to 12: Preparation of toner)
A toner and a two-component developer were obtained and evaluated in the same manner as in Example 1 except that resins A to D and release agents W1 to W3 were used in the mixing ratios shown in Tables 5 and 6.

<Evaluation>
The external additive toners and two-component developers prepared in Examples 1 to 27 and Comparative Examples 1 to 22 were evaluated with respect to the following items, and a comprehensive evaluation was made based on the results.

<Evaluation of magnet roller seizure>
The external additive toner and the two-component developer are filled in a developing device and a toner cartridge of a commercially available color multifunction machine (manufactured by Sharp Corporation, model: BP-20C25). Then, the temperature and humidity were adjusted to 30° C. so that a square solid image (ID=1.45 to 1.50) with a side of 10 mm was formed at three points in the axial direction of the developing roller: the center and both ends. A continuous print test of 50,000 sheets of A4 paper is performed under an environment of 80%. At that time, the image density at the initial stage and after 50,000 sheets was measured using a colorimetric color difference meter (spectral densitometer, manufactured by X-Rite, model: 504). Measure the difference (ΔID).

Based on the obtained results, the seizure phenomenon is evaluated according to the following criteria.
◎ (excellent): no density decrease (ΔID is less than 0.1) and
No fusion of toner on the surface of the developing roller ◯ (good): no decrease in density (ΔID is less than 0.1) and
Fusion of toner is observed on the developing roller surface.
Fusion of toner is observed on the surface of the developing roller.
Toner fusion is observed on the surface of the developing roller

<Fixability>
Using a commercially available copying machine (manufactured by Sharp Corporation, model: MX-6171) modified for evaluation, a fixed image is produced with a two-component developer.
First, a sample image including a solid image portion (a rectangle of 20 mm in length and 50 mm in width) was recorded on a recording paper (manufactured by Sharp Corporation, PPC paper, model: SF-4AM3). An unfixed image is formed by adjusting the amount to 0.5 mg/cm ² .
Next, a fixed image is produced using a belt fixing device. The fixing process speed is set to 200 mm/sec, the temperature of the fixing belt is increased from 130° C. by 5° C., and gloss measurement and fixability determination are performed at each fixing temperature.
Fixability is evaluated by finding a temperature range in which neither low-temperature offset nor high-temperature offset occurs, the upper limit of which is defined as the "fixing upper limit temperature", and the lower limit of which is defined as the "fixing lower limit temperature".
"High-temperature offset" and "low-temperature offset" are defined as toner that does not fuse to the recording paper during fixation, and adheres to the recording paper after the fixing belt completes one turn while adhering to the fixing belt.

Based on the obtained results, the maximum fixing temperature is evaluated according to the following criteria.
◎ (very good): upper limit fixing temperature is 200°C or higher ○ (good): upper limit fixing temperature is 190°C or higher and lower than 200°C △ (slightly poor): upper limit fixing temperature is lower than 180°C or higher and lower than 190°C × (poor): Maximum fixing temperature is less than 180°C

Also, based on the obtained results, the minimum fixing temperature is evaluated according to the following criteria.
◎ (very good): minimum fixing temperature is less than 130°C ○ (good): minimum fixing temperature is 130°C or more and less than 140°C △ (slightly poor): minimum fixing temperature is less than 140°C or more and less than 150°C × (poor): Minimum fixing temperature is 150°C or higher

<Comprehensive evaluation>
Based on the above evaluation results, comprehensive judgment was made according to the following criteria.
◎ (Excellent): All evaluation items are ◎ (usable)
○ (Good): ○ even for one evaluation item (can be used)
△ (Possible): Even one evaluation item has a △ (can be used)
× (impossible): Even one evaluation item has an × (cannot be used)

Tables 5 and 6 show the physical properties and compounding ratios of the resins and release agents constituting the toners of Examples and Comparative Examples, and Table 7 shows the evaluation results of the toners and developers of Examples and Comparative Examples.
The items and abbreviations in Tables 5 and 6 mean the following, respectively.
Materials: A1 to A9, B1 to B9, C1 to C9, D1 to D9 of each resin, W1 to W3 of each wax
SP: Resin solubility parameter SP value ((cal/cm ³ ) ^1/2 )
Tm: Melting temperature of resin (°C)
Proportion: mass ratio (% by mass) in toner base particles
The total amount of resins A to D is 92% by mass, and the other components are additive components Material ratio: mass ratio of resins B and C, resins C and D Type: type of mold release agent (E: ester wax, P: paraffin type wax)
Structure: Molecular structure of release agent (SC: linear structure, SS: steric structure)

The results in Table 1 reveal the following.
(1) Although the toner of the present invention has superiority and inferiority, it is possible to provide a toner and a two-component developer containing the same that are resistant to image sticking over a long period of time and have excellent hot offset resistance and low temperature fixability ( Examples 1-27)
(2) The toner of the present invention exhibits excellent effects when the SP value of resin A is in the range of 10.85 to 11.20 (cal/cm ³ ) ^1/2 (Examples 1 and 2 to 3). , see Comparative Examples 1 and 2)
(3) The toner of the present invention exhibits excellent effects when the melting temperature Tm of the resin A is in the range of 90 to 110° C. (see Examples 1 and 4 to 5 and Comparative Examples 3 to 4).
(4) The toner of the present invention exhibits excellent effects when the SP value of resin B is in the range of 10.85 to 11.20 (cal/cm ³ ) ^1/2 (Examples 1 and 6 to 7). , see Comparative Examples 5-6)
(5) The toner of the present invention exhibits excellent effects when the melting temperature Tm of the resin B is in the range of 130 to 150° C. (see Examples 1 and 8 to 9 and Comparative Examples 7 to 8).
(6) The toner of the present invention exhibits excellent effects when the SP value of resin C is in the range of 10.50 to 10.80 (cal/cm ³ ) ^1/2 (Examples 1 and 10 to 11 , see Comparative Examples 9-10)
(7) The toner of the present invention exhibits excellent effects when the melting temperature Tm of the resin C is in the range of 125 to 145° C. (see Examples 1 and 12 and 13 and Comparative Examples 11 and 12).
(8) The toner of the present invention exhibits excellent effects when the SP value of Resin D is in the range of 9.40 to 9.60 (cal/cm ³ ) ^1/2 (Examples 1 and 14 to 17 reference)
(9) The toner of the present invention exhibits excellent effects when the mass ratio B/C of resin B and resin C is in the range of 1.5 to 6.0 (Examples 1, 18 to 19 and 22 ~23 reference)
(10) The toner of the present invention exhibits excellent effects when the mass ratio C/D of resin C and resin D is in the range of 1.0 to 5.0 (Examples 1, 20 to 21 and 24 ~25 reference)
(11) The toner of the present invention exhibits excellent effects when the releasing agent is an ester wax (see Examples 1 and 26).
(12) The toner of the present invention exhibits excellent effects when the release agent has an ester component with a linear molecular structure (see Examples 1 and 27).

Claims (7)

A toner having toner particles comprising a resin, a colorant and a release agent,
The resin is an amorphous resin composed of an amorphous resin A containing polyester as a main component, an amorphous resin B containing polyester as a main component, and a hybrid resin C containing a polyester portion and a vinyl copolymer portion, and Containing a crystalline resin D containing polyester as a main component,
The amorphous resin A has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 90 to 110°C,
The amorphous resin B has an SP value of 10.85 to 11.20 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 130 to 150°C,
A toner, wherein the hybrid resin C has an SP value of 10.50 to 10.80 (cal/cm ³ ) ^1/2 and a melting temperature Tm of 125 to 145°C. 2. The toner according to claim 1, wherein the crystalline resin D has an SP value of 9.40 to 9.60 (cal/cm ³ ) ^1/2 . 3. The toner according to claim 1, wherein the mass ratio B/C of the amorphous resin B and the amorphous resin C is 1.5 to 6.0. The toner according to any one of claims 1 to 3, wherein the mass ratio C/D between the hybrid resin C and the crystalline resin D is 1.0 to 5.0. The toner according to any one of claims 1 to 4, wherein the release agent is an ester wax. 6. The toner according to claim 5, wherein the ester wax is a wax having an ester component with a linear molecular structure. A two-component developer comprising the toner according to any one of claims 1 to 6 and a carrier.