JP7171358B2 - Toner for electrostatic charge image development - Google Patents

Description

The present invention relates to an electrostatic image developing toner and the like used for developing a latent image formed by an electrophotography method, an electrostatic recording method, an electrostatic printing method, or the like.

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving higher image quality and higher speed.

Patent Document 1 discloses a toner for electrostatic image development containing a phosphonic acid-based sequestering agent, which contains a crystalline resin and a non-crystalline resin as a binder resin of the toner, wherein the non-crystalline resin comprises a high molecular weight component. Example 1 describes a toner containing n-octadecenylsuccinic acid as a constituent monomer of the high and low molecular weight components, which are amorphous polyester resins. It is described that the toner can form high-quality images over a long period of time.

In Patent Document 2, a core containing polyester, a mold release agent and a colorant, and containing a polyester produced using a dicarboxylic acid having an alkyl group having 8 to 20 carbon atoms as a polymerization component, and the core and a coating portion containing a polymer of a vinyl-based monomer, which is coated with a toner for developing an electrostatic charge image. It is described that image omission is less likely to occur with this toner.

JP 2009-271173 A JP 2014-38177 A

However, with the toners described in Patent Documents 1 and 2, it is difficult to obtain a toner for electrostatic charge image development that exhibits excellent low-temperature fixability and excellent heat-resistant storage stability, and it is also required to exhibit excellent glossiness. had been
Accordingly, the present invention relates to a toner for electrostatic charge image development, which is excellent in low-temperature fixability, excellent heat-resistant storage stability, and excellent glossiness.

The present inventors used a toner containing an amorphous polyester resin and a crystalline polyester resin, and found that the carboxylic acid component of the amorphous polyester resin is a linear aliphatic hydrocarbon group having 16 or more and 18 or less carbon atoms. contains succinic acid or its anhydride substituted with , contains an aliphatic diol having 4 to 8 carbon atoms as the alcohol component of the crystalline polyester resin, and contains 4 to 6 carbon atoms as the carboxylic acid component of the crystalline polyester resin It has been found that an electrostatic charge image developing toner having excellent low-temperature fixability, excellent heat-resistant storage stability, and excellent glossiness can be obtained by containing an aliphatic dicarboxylic acid.
The present invention contains an amorphous polyester resin and a crystalline polyester resin,
The amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms,
The electrostatic charge image, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing an aliphatic diol having 4 to 8 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 6 carbon atoms. It relates to toner for development.

According to the present invention, it is possible to provide an electrostatic charge image developing toner which is excellent in low-temperature fixability and heat-resistant storage stability, and which is excellent in glossiness.

[Electrostatic charge image developing toner]
The toner for electrostatic charge image development of the present invention (hereinafter also referred to as "toner") comprises an amorphous polyester resin (hereinafter also simply referred to as "resin A") and a crystalline polyester resin (hereinafter simply referred to as "resin C"). (also referred to as
The amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms,
The crystalline polyester resin is a polycondensate of an alcohol component containing an aliphatic diol having 4 to 8 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 6 carbon atoms.
According to the above configuration, it is possible to obtain a toner for developing an electrostatic charge image which is excellent in low-temperature fixability and heat-resistant storage stability, and which is excellent in glossiness.

Although the reason why the toner of the present invention is excellent in low-temperature fixability, excellent heat-resistant storage stability, and excellent glossiness is not clear, it is considered as follows.
The toner of the present invention comprises an amorphous polyester resin containing, as a carboxylic acid component in the amorphous polyester resin, succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms or an anhydride thereof, and crystals. contains synthetic polyester.
By including a unit derived from succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group that has a high affinity with the crystalline polyester in the polymer chain of the amorphous polyester resin, the crystalline polyester in the toner is improved. It is believed that the improved dispersibility results in excellent low-temperature fixability.
The crystalline polyester resin is a polycondensate of an alcohol component containing an aliphatic diol having 4 to 8 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 6 carbon atoms. Therefore, as a carboxylic acid component, a local interaction with an amorphous polyester resin containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 or more and 18 or less carbon atoms is expressed, This interaction promotes crystallization, and as a result, the heat-resistant storage stability of the toner is considered to be excellent. Furthermore, the plasticization of the amorphous polyester by the crystalline polyester is accelerated, the viscosity of the toner during fixation tends to decrease, and a smooth printed surface is obtained, resulting in excellent glossiness.

Definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum temperature of the endothermic peak (softening point (°C)/maximum temperature of the endothermic peak (°C)) in the measurement method described in Examples below. A crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. Amorphous resins are those with a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate.
The maximum temperature of the endothermic peak refers to the temperature of the highest endothermic peak among the observed endothermic peaks. The crystallinity index is calculated from the values obtained by measuring the softening point of the resin and the maximum endothermic peak temperature described in Examples.
In the specification, the carboxylic acid component of the polyester resin includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (the number of carbon atoms in the alkyl group is 1 or more and 3 or less). is also included.
In the specification, the term "binder resin" is a general term for resin components contained in a toner containing an amorphous polyester resin and a crystalline polyester resin.

[Toner particles]
Toner includes, for example, toner particles. The toner particles preferably contain an amorphous polyester resin and a crystalline polyester resin, which will be described later. Toner particles contain additives such as release agents, colorants, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, and cleaning improvers. It may contain a release agent, a colorant, and a charge control agent, preferably.

<Amorphous polyester resin>
The amorphous polyester resin is substituted with an alcohol component and a linear aliphatic hydrocarbon group having 16 or more and 18 or less carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixability and heat-resistant storage stability and excellent glossiness. It is a polycondensate with a carboxylic acid component containing succinic acid or its anhydride. In this specification, the alcohol component in the amorphous polyester resin is referred to as "alcohol component (A-al)", and the carboxylic acid component in the amorphous polyester resin is referred to as "carboxylic acid component (A-ac)". There is

(Alcohol component (A-al))
Examples of the alcohol component (A-al) include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols or linear or branched aliphatic diols are preferred, and aromatic diols are more preferred.
The amount of the aromatic diol in the alcohol component (A-al) is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, More preferably, it is 100 mol %.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an oxide adduct. These may be used alone or in combination of two or more.
As the alkylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A are preferable.
The amount of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, in the alcohol component, and 100 mol % or less, more preferably 100 mol %.

Examples of linear or branched aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol. , 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 12-dodecanediol.
Among these, branched aliphatic diols are preferred. Branched aliphatic diols include, for example, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol is mentioned. Among these, 1,2-propanediol is more preferable.
When a branched aliphatic diol is included as the alcohol component (A-al), the amount of the branched aliphatic diol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol. % or more and 100 mol % or less, more preferably 100 mol %.

Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane], alkylene oxide of hydrogenated bisphenol A having 2 to 4 carbon atoms (average addition mole number 2 to 12 below) adducts.
Examples of trihydric or higher polyhydric alcohols include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components (A-al) may be used.

(Carboxylic acid component (A-ac))
The carboxylic acid component (A-ac) is substituted with a linear aliphatic hydrocarbon group having 16 or more and 18 or less carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixability and heat-resistant storage stability and excellent glossiness. succinic acid or its anhydride.
A linear aliphatic hydrocarbon group may be either unsaturated or saturated. Among these, straight-chain unsaturated aliphatic hydrocarbon groups are preferred.
The number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 16 or 18 from the viewpoint of availability.
Examples of the succinic acid or anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms include hexadecenylsuccinic acid, octadecenylsuccinic acid and anhydrides thereof. .

Carboxylic acid component (A-ac) is succinic acid or anhydride substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms and succinic acid or anhydride substituted with a straight-chain aliphatic hydrocarbon group having 18 carbon atoms. It is preferred to include things.
In the carboxylic acid component (A-ac), succinic acid or its anhydride substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms and succinic acid or its anhydride substituted with a straight-chain aliphatic hydrocarbon group having 18 carbon atoms The molar ratio [(C16/C18) molar ratio] is preferably 30/70 or more, more preferably 35/65 or more, and still more preferably 40 from the viewpoint of obtaining a toner having excellent heat-resistant storage stability and glossiness. /60 or more, more preferably 50/50 or more, and preferably 70/30 or less, more preferably 65/35 or less, still more preferably 60/40 or less.

In the carboxylic acid component (A-ac), the ratio of succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms is based on 100 mol parts of the alcohol component (A-al). , preferably 1 mol part or more, more preferably 3 mol parts or more, still more preferably 5 mol parts or more, still more preferably 8 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less , more preferably 30 mol parts or less, more preferably 20 mol parts or less, still more preferably 12 mol parts or less.
In the carboxylic acid component (A-ac), the amount of succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, still more preferably is 30 mol % or less, more preferably 20 mol % or less, still more preferably 12 mol % or less.

The carboxylic acid component (A-ac) may contain, for example, other dicarboxylic acids and polycarboxylic acids having a valence of 3 or more.
Other dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids ( hereinafter also referred to as "other linear or branched aliphatic dicarboxylic acids") and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and other linear or branched aliphatic dicarboxylic acids is preferable, and aromatic dicarboxylic acids are more preferable.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component (A-ac) is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol%. Below, more preferably 80 mol % or less, still more preferably 75 mol % or less.

The other linear or branched aliphatic dicarboxylic acids preferably have 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less carbon atoms, more preferably 20 or less carbon atoms.
Other linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, Azelaic acid is mentioned. Among these, fumaric acid, adipic acid and sebacic acid are preferred.
The amount of other linear or branched aliphatic dicarboxylic acids in the carboxylic acid component (A-ac) is preferably 1 mol% or more, more preferably 10 mol% or more, and preferably 40 mol% or less. , more preferably 30 mol % or less.

The amorphous polyester resin preferably contains a trivalent or higher polyvalent carboxylic acid as a carboxylic acid component. The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, more preferably trimellitic acid or its anhydride.
The amount of trivalent or higher polycarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more in the carboxylic acid component (A-ac), and is preferably is 40 mol % or less, more preferably 30 mol % or less, still more preferably 20 mol % or less.
One or more of these carboxylic acid components (A-ac) may be used.

The equivalent ratio [COOH group/OH group] of the carboxy group of the carboxylic acid component (A-ac) to the hydroxyl group of the alcohol component (A-al) is preferably 0.7 or more, more preferably 0.8 or more, And it is preferably 1.3 or less, more preferably 1.2 or less.

(Production of amorphous polyester resin)
The amorphous polyester resin may be produced, for example, by a method including a step of conducting a polycondensation reaction with the alcohol component (A-al) and the carboxylic acid component (A-ac).
In this step, if necessary, an esterification catalyst such as di(2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamine, etc. is added to the alcohol component and the carboxylic acid component in a total amount of 100. 0.01 parts by mass or more and 5 parts by mass or less per part by mass; Esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid), total amount of alcohol component and carboxylic acid component is 100 mass 0.001 parts by mass or more and 0.5 parts by mass or less may be used for polycondensation.
Further, when a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. More than 0.5 parts by mass or less of the radical polymerization inhibitor may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

(Physical properties of amorphous polyester resin)
The softening point of the amorphous polyester resin is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, still more preferably 110° C. or higher, still more preferably 112° C. or higher. It is 140° C. or lower, more preferably 130° C. or lower, and still more preferably 125° C. or lower.
The glass transition temperature of the amorphous polyester resin is preferably 30° C. or higher, more preferably 40° C. or higher, still more preferably 50° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower, and still more preferably. is below 60°C.

The acid value of the amorphous polyester resin is preferably 5 mgKOH/g or more, more preferably 8 mgKOH/g or more, still more preferably 10 mgKOH/g or more, and preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g. Below, more preferably 30 mgKOH/g or less.

The number average molecular weight of the amorphous polyester resin is preferably 3,000 or more, more preferably 3,500 or more, still more preferably 4,000 or more, and preferably 8,000 or less, more preferably 6,000 or more. 000 or less, more preferably 5,000 or less.

The weight average molecular weight of the amorphous polyester resin is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, and preferably 1,000,000 or less, more preferably 800,000 or less, more preferably 100,000 or less.

The softening point, glass transition temperature, acid value, number-average molecular weight and weight-average molecular weight of the amorphous polyester resin are appropriately adjusted according to the type and amount of raw material monomers used, and production conditions such as reaction temperature, reaction time and cooling rate. and their values are determined by the method described in the Examples. When two or more amorphous polyester resins are used in combination, the softening point, glass transition temperature, and acid value obtained as a mixture thereof are preferably within the ranges described above.

<Crystalline polyester resin>
The toner contains a crystalline polyester resin from the viewpoint of improving low-temperature fixability and glossiness.
The crystalline polyester resin is a polycondensate of an alcohol component containing an aliphatic diol having 4 to 8 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 6 carbon atoms. In this specification, the alcohol component in the crystalline polyester resin may be referred to as "alcohol component (C-al)", and the carboxylic acid component in the crystalline polyester resin may be referred to as "carboxylic acid component (C-ac)". .

(Alcohol component (C-al))
The alcohol component (C-al) contains an aliphatic diol having 4 to 8 carbon atoms, preferably an α,ω-aliphatic diol having 4 to 8 carbon atoms. One or two or more aliphatic diols having 4 to 8 carbon atoms may be used.
The number of carbon atoms in the aliphatic diol having 4 or more and 8 or less carbon atoms is preferably 4 or more and preferably 6 or less.
Examples of aliphatic diols having 4 to 8 carbon atoms include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. and α,ω-aliphatic diols other than α,ω-aliphatic diols such as neopentyl glycol. Among these, 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol are preferred, 1,4-butanediol and 1,6-hexanediol are more preferred, and 1,6-hexanediol is preferred. is more preferred.

The amount of the aliphatic diol having 4 to 8 carbon atoms is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, in the alcohol component (C-al). mol % or more and 100 mol % or less, more preferably 100 mol %.

The alcohol component (C-al) may contain other alcohol components different from the aliphatic diol having 4 to 8 carbon atoms. Other alcohol components include, for example, ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12 - Aliphatic diols having 2 to 3 or 9 to 14 carbon atoms such as dodecanediol, 1,13-tridecanediol, and 1,14-tetradecanediol; aromatic diols such as alkylene oxide adducts of bisphenol A; Trihydric or higher alcohols such as glycerin, pentaerythritol and trimethylolpropane are included. One or more of these alcohol components (C-al) may be used.

(Carboxylic acid component (C-ac))
The carboxylic acid component (C-ac) contains an aliphatic dicarboxylic acid having 4 to 6 carbon atoms. One or two or more aliphatic dicarboxylic acids having 4 to 6 carbon atoms may be used.
The number of carbon atoms in the aliphatic dicarboxylic acid having 4 to 6 carbon atoms is preferably 4.
Examples of aliphatic dicarboxylic acids having 4 to 6 carbon atoms include fumaric acid, succinic acid, glutaric acid, and adipic acid. Among these, fumaric acid and succinic acid are preferred.

The amount of the aliphatic dicarboxylic acid having 4 to 6 carbon atoms in the carboxylic acid component (C-ac) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably is 95 mol % or more and 100 mol % or less, more preferably 100 mol %.

The carboxylic acid component (C-ac) may contain a carboxylic acid component different from the aliphatic dicarboxylic acid having 4 to 6 carbon atoms. Other carboxylic acid components include, for example, aliphatic dicarboxylic acids having 7 to 14 carbon atoms such as sebacic acid, dodecanedioic acid, and tetradecanedioic acid; aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; A polyhydric carboxylic acid is mentioned. One or more of these carboxylic acid components (C-ac) may be used.

The equivalent ratio (COOH group/OH group) of the carboxy group of the carboxylic acid component (C-ac) to the hydroxyl group of the alcohol component (C-al) is preferably 0.7 or more, more preferably 0.8 or more, And it is preferably 1.3 or less, more preferably 1.2 or less.

(Physical properties of crystalline polyester resin)
The softening point of the crystalline polyester resin is preferably 60° C. or higher, more preferably 70° C. or higher, still more preferably 75° C. or higher, and still more preferably 80° C. or higher, from the viewpoint of further improving heat-resistant storage stability, and It is preferably 150° C. or lower, more preferably 140° C. or lower, from the viewpoint of further improving low-temperature fixability.

The melting point of the crystalline polyester resin is preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 70° C. or higher, from the viewpoint of further improving heat-resistant storage stability, and from the viewpoint of further improving low-temperature fixability. Therefore, it is preferably 150° C. or lower, more preferably 140° C. or lower.

The acid value of the crystalline polyester resin is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and preferably 35 mgKOH/g or less, more preferably 30 mgKOH/g or less, still more preferably 25 mgKOH/g or less. is.

The softening point, melting point, and acid value of the crystalline polyester resin can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples below. When two or more crystalline polyester resins are used in combination, the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the ranges described above.

A crystalline polyester resin is obtained, for example, by polycondensation of an alcohol component (C-al) and a carboxylic acid component (C-ac). For the polycondensation conditions, for example, the conditions shown in the polycondensation of the amorphous polyester resin described above can be applied.

The mass ratio [resin A/resin C] of the amorphous polyester resin and the crystalline polyester resin is preferably 80/20 or more, more preferably 85/15 or more, more preferably 87/13 or more, and It is preferably 99/1 or less, more preferably 95/5 or less, and still more preferably 92/8 or less.

In the resin component of the toner, the total content of the amorphous polyester resin and the crystalline polyester resin [resin A + resin C] is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. and not more than 100% by mass, preferably 100% by mass.

<Release agent>
Wax is preferred as the release agent.
Waxes include, for example, hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.
Hydrocarbon waxes include, for example, mineral or petroleum hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax; synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of ester waxes include mineral or petroleum ester waxes such as montan wax; vegetable ester waxes such as carnauba wax, rice wax and candelilla wax; and animal ester waxes such as beeswax.
Fatty acid amide waxes include, for example, oleic acid amide and stearic acid amide. A release agent can be used individually or in combination of 2 or more types.
Among these, hydrocarbon waxes are preferred, and paraffin waxes are more preferred, from the viewpoint of widening the fixation range and further improving heat resistance stability.

The melting point of the releasing agent is preferably 60° C. or higher, more preferably 70° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, and still more preferably 140° C. or lower.
The method for measuring the melting point of the release agent is according to the method described in Examples.

The amount of the release agent is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass as the total amount of Resin A and Resin C, and , preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

<Colorant>
Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. mentioned.
A coloring agent can be used individually or in combination of 2 or more types.
The toner may be black toner or color toner other than black.
From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the total amount of Resin A and Resin C, and , preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

<Charge control agent>
The charge control agent may contain either a positive charge control agent or a negative charge control agent.
Examples of positive charge control agents include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives, and styrene-acrylic resins.
Examples of nigrosine dyes include "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron N-01", "Bontron N-04", "Bontron N-07", and "Bontron N-09." ” and “Bontron N-11” (manufactured by Orient Chemical Industry Co., Ltd.). Examples of quaternary ammonium salt compounds include "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX VP435" (manufactured by Clariant). Examples of polyamine resins include "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.). Examples of imidazole derivatives include "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Co., Ltd.). Examples of the styrene-acrylic resin include "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.).

Examples of negative charge control agents include metal-containing azo dyes, metal compounds of benzilic acid compounds, metal compounds of salicylic acid compounds, copper phthalocyanine dyes, quaternary ammonium salts, nitroimidazole derivatives, and organometallic compounds.
Examples of metal-containing azo dyes include "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" (Orient Chemical Industry Co., Ltd. (manufactured by Hodogaya Chemical Industry Co., Ltd.), “Eizenspiron Black TRH”, and “T-77” (manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of metal compounds of benzylic acid compounds include "LR-147" and "LR-297" (manufactured by Nihon Carlit Co., Ltd.). Examples of metal compounds of salicylic acid compounds include "Bontron E-81", "Bontron E-84", "Bontron E-88", "Bontron E-304" (manufactured by Orient Chemical Industry Co., Ltd.), "TN -105” (manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of quaternary ammonium salts include "COPY CHARGE NX VP434" (manufactured by Clariant). Examples of organometallic compounds include "TN105" (manufactured by Hodogaya Chemical Industry Co., Ltd.).
Among charge control agents, negative charge control agents are preferable, and metal compounds of salicylic acid compounds are more preferable.
A charge control agent can be used individually or in combination of 2 or more types.

The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.3 parts by mass with respect to 100 parts by mass of the total amount of Resin A and Resin C. and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less.

The toner may be a chemical toner obtained by an emulsion aggregation method, or may be a pulverized toner obtained by a melt-kneading method.
If it is a chemical toner, the toner preferably comprises core-shell toner particles having a core and a shell located on the surface of the core.
The core preferably contains resin A, resin C and a release agent, and may contain additives as necessary.
The shell preferably contains resin A. Also, the shell preferably covers the surface of the core.
The content of resin A contained in the shell is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and still more preferably 10 parts by mass with respect to 100 parts by mass as the total content of resin A and resin C contained in the core. It is at least 30 parts by mass, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

<Physical properties of toner particles>
The volume-median particle diameter ( _D50 ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more, from the viewpoint of obtaining high-quality images and further improving the cleanability of the toner. Yes, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm or less.
The volume-median particle size ( _D50 ) of toner particles can be measured by the method described in Examples.

[External additive]
Although the toner particles can be used as the toner as it is, it is preferable to use the toner after adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
Examples of external additives include inorganic material fine particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
When the toner particles are surface-treated using an external additive, the amount of the external additive added is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less.

Toners are used for electrostatic image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.

[Production method]
The toner may be a toner obtained by any method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, or an aggregation-fusion method. The chemical toner obtained by the adhesion method and the pulverized toner obtained by the melt-kneading method are preferable, and the pulverized toner obtained by the melt-kneading method are more preferable.

[Aggregation and fusion method]
In the case of a chemical toner produced by the aggregation fusion method, the method for producing the toner includes, for example,
A step of aggregating resin particles containing resin A in the same or different particles, optionally resin particles containing resin C, and release agent particles to obtain aggregated particles (1) (hereinafter referred to as “step 1 ”),
A step of attaching resin particles containing resin A in the same or different particles to aggregated particles (1) to obtain aggregated particles (2) (hereinafter also referred to as “step 2”); The step of fusing with (hereinafter also referred to as “step 3”)
including.

Various resin particles used in step 1 are dispersions obtained by dispersing resins such as resin A and resin C in advance in an aqueous medium. Although the dispersion method is not particularly limited, it is preferable to disperse by, for example, a phase inversion emulsification method. The phase inversion emulsification method includes, for example, a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to effect phase inversion emulsification. The aqueous medium preferably contains water as a main component, and the content of water in the aqueous medium is, for example, 80% by mass or more and 100% by mass or less. The aqueous medium may contain a water-soluble organic solvent.
As the release agent particles used in step 1, a dispersion liquid in which the release agent is previously dispersed by a known method may be used. In step 1, the various additives described above may be aggregated.
In step 1, for example, in the presence of a surfactant such as alkylbenzenesulfonate, the dispersion is mixed, a flocculating agent such as ammonium sulfate is added to flocculate, and if necessary, flocculation of the surfactant or the like. Aggregated particles (1) are obtained by adding a terminating agent.

In step 2, a resin particle dispersion containing resin A is added to the system containing the aggregated particles (1), whereby the resin particles containing resin A are adhered to the aggregated particles (1), and aggregated. Particles (2) are obtained. Aggregation can be carried out in the same manner as in step 1.
In step 3, aggregated particles (2) are fused in an aqueous medium. By fusion, each particle contained in the aggregated particles is fused to obtain fused particles.
Post-treatment may be performed after step 3. For example, toner particles are obtained by solid-liquid separation of the fused particles present in the aqueous medium and drying. Further, the toner particles may be added with the above external additives.

[Melt-kneading method]
In the case of the pulverized toner by the melt-kneading method, raw materials such as resin A, resin C, release agent, colorant, charge control agent, etc. are uniformly mixed with a mixer such as a Henschel mixer, a ball mill, etc., followed by a closed kneader, It can be produced by melt-kneading with a single-screw or twin-screw extruder, an open-roll type kneader, or the like, followed by cooling, pulverization, and classification.
The method of producing toner by the melt-kneading method preferably includes a step of melt-kneading a mixture containing resins such as resin A and resin C as binder resins at a temperature in the range of 80° C. or higher and 160° C. or lower. The melt-kneading temperature is preferably 85° C. or higher, more preferably 90° C. or higher, and preferably 150° C. or lower, more preferably 145° C. or lower.
In the binder resin composition containing resins such as resin A and resin C, the affinity between the amorphous resin and the crystalline resin is high, but they are difficult to be compatible with each other and are finely dispersed in the amorphous resin. Since the crystallinity of the crystalline resin that may be present is also good, the binder resin can be crystallized by the melt-kneading step described above.

The method for producing the toner preferably includes a step of cooling the mixture obtained by melt-kneading to an extent that pulverization is possible, followed by pulverization and classification to obtain toner particles. Pulverization may be performed in multiple stages. For example, after the mixture obtained by melt-kneading is coarsely pulverized to 1 mm or more and 5 mm or less, it may be further finely pulverized to a desired particle size.
Pulverizers suitable for coarse pulverization include, for example, a hammer mill, an atomizer, and a Rotoplex. Pulverizers suitably used for fine pulverization include, for example, fluidized bed jet mills, impingement plate jet mills, and rotary mechanical mills. From the viewpoint of pulverization efficiency, it is preferable to use a fluidized bed jet mill and a collision plate jet mill.
Classifiers used for classification include, for example, rotor classifiers, air classifiers, inertial classifiers, and sieve classifiers. In the classification step, the pulverized material removed due to insufficient pulverization may be subjected to the pulverization step again, and the pulverization step and the classification step may be repeated as necessary.

Properties of the resin, resin particles, toner, etc. were measured and evaluated by the following methods.

[Acid value of resin]
The acid value of the resin was measured according to JIS K 0070:1992. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070:1992 to a mixed solvent of acetone and toluene (acetone:toluene=1:1 (volume ratio)).

[Resin softening point, glass transition temperature, etc.]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.
(2) Maximum temperature of endothermic peak Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), the temperature was lowered from room temperature (20 ° C.) to 0 ° C. at a cooling rate of 10 ° C./min. The sample cooled to the temperature was allowed to stand still for 1 minute, and then the calorific value was measured while the temperature was raised to 180°C at a heating rate of 10°C/min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side was taken as the maximum temperature of the endothermic peak.
For the crystalline polyester resin, the maximum temperature of the endothermic peak was taken as the melting point of the crystalline polyester resin.
(3) Glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample is weighed in an aluminum pan and heated to 200 ° C. and cooled to 0°C from that temperature at a cooling rate of 10°C/min. Next, the calorie was measured while the temperature was raised to 150° C. at a temperature elevation rate of 10° C./min. In the case of an amorphous resin, the glass transition temperature was defined as the temperature at the intersection of the extended line of the baseline below the maximum temperature of the endothermic peak and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak.

[Number average molecular weight and weight average molecular weight of polyester resin]
The molecular weight distribution was measured by gel permeation chromatography (GPC) by the following method, and the number average molecular weight Mn and weight average molecular weight Mw of the resin were obtained.
(1) Preparation of Sample Solution A polyester resin was dissolved in chloroform so as to have a concentration of 0.5 g/100 mL. Then, this solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, chloroform was passed as an eluent at a flow rate of 1 mL/min, and the column was stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution was injected thereinto and measured. The molecular weight of the sample was calculated based on a previously prepared calibration curve. The calibration curve at this time includes several types of monodisperse polystyrene with known molecular weights (manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ ; 2.10×10 ³ , 7.00×10 ³ , 5.04×10 ⁴ ) were used as standard samples.
Measuring device: "CO-8010" (manufactured by Tosoh Corporation)
Analysis column: "GMH _XL " + "G3000H _XL " (manufactured by Tosoh Corporation)

[Melting point of release agent]
Using a differential scanning calorimeter "DSC Q20" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, and heated to 200 at a heating rate of 10 ° C./min. °C, and then cooled to -10°C at a cooling rate of 5°C/min. Next, the sample is heated to 180° C. at a heating rate of 10° C./min and measured. The maximum endothermic peak temperature observed from the melting endothermic curve thus obtained is taken as the melting point of the release agent.

[Volume Median Particle Diameter of Toner Particles ( _D50 )]
The volume median particle size of the toner particles was measured as follows.
・Measuring machine: "Coulter Multisizer III" (manufactured by Beckman Coulter, Inc.)
・Aperture diameter: 50 μm
・ Analysis software: "Multisizer III version 3.51" (manufactured by Beckman Coulter, Inc.)
・Electrolyte: “Isoton II” (manufactured by Beckman Coulter, Inc.)
- Dispersion: Polyoxyethylene lauryl ether "Emulgen 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of a toner measurement sample was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and dispersed for 1 minute with an ultrasonic disperser. , to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, then 30,000 particles are measured, and the particle size distribution The volume median particle size (D ₅₀ ) was obtained from

[Low Temperature Fixability of Toner]
Toner was mounted on a copier "AR-505" (manufactured by Sharp Corporation) in which the fixing device was improved so that it could be fixed outside the device, and printed matter was obtained in an unfixed state (printing area: 2 cm) × 12 cm, adhesion amount: 0.5 mg/cm ² ). After that, using a fixing machine (fixing speed: 300 mm/sec) adjusted so that the total fixing pressure was 40 kgf, the temperature of the fixing roll was increased from 100° C. to 240° C. by 5° C. in increments of 5° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape "Unicef cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522: 2009) was attached to the image portion of the resulting printed matter, and the temperature was set to 30 ° C. separately from the fixing roll of the fixing machine. After passing through the fixing roller, the tape was peeled off. The optical reflection density before the tape was applied and after it was removed was measured using a reflection densitometer "RD-915" (manufactured by Gretag Macbeth), and the ratio of the two (after peeling/before pasting x 100) was initially 90%. was taken as the lowest fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability. As the fixing paper, "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/m ² ) was used.

[Heat-resistant storage stability of toner]
10 g of toner was placed in a 50 mL plastic cup and held for 24 hours under an environment of a temperature of 50° C. and a relative humidity of 60%. After that, on a powder tester (manufactured by Hosokawa Micron Corporation), three sieves, sieve A (opening 250 μm), sieve B (opening 150 μm), and sieve C (opening 75 μm) are placed in order from the top, 10 g of toner was put on the sieve A and shaken for 60 seconds. Next, α obtained from the following formula was calculated to evaluate fluidity. The larger the α value, the better the heat resistance storage.

α=100−[(mass of toner remaining on sieve A (g))+(mass of toner remaining on sieve B (g))×0.6+(mass of toner remaining on sieve C (g))× 0.2]/10 (g) x 100

[Glossiness of printed matter]
Toner was mounted on a copying machine "AR-505" (manufactured by Sharp Corporation), and a solid image was taken out before passing through the fixing machine to obtain a printed matter in an unfixed state (printing area: 2 cm × 12 cm, adhesion amount : 0.5 mg/cm ² ). Next, the fixing machine of the copier was used off-line to fix at 150° C. and 300 mm/sec to obtain a printed matter. J paper (manufactured by Fuji Xerox Co., Ltd.) was used as the printing medium.
The glossiness of the resulting printed matter was measured using a gloss meter "IG-330" (manufactured by HORIBA, Ltd.) with a cardboard under the image and a light irradiation condition of 60°. A higher value indicates a higher glossiness.

[Production of alkenyl succinic anhydride]
Production Example a (Production of alkenyl succinic anhydride (a))
273.5 g of α-olefin “Linearene 16” (manufactured by Idemitsu Kosan Co., Ltd., C16 α-olefin), α-olefin “Linearene 18” (manufactured by Idemitsu Kosan Co., Ltd., C18 α-olefin) 253 in a 1 L autoclave manufactured by Nitto Koatsu Co., Ltd. 9 g, 157.2 g of maleic anhydride, 0.4 g of antioxidant "Chelex-O" (manufactured by SC Organic Chemical Co., Ltd., triisooctyl phosphite), and 0.1 g of butyl hydroquinone as a polymerization inhibitor, were charged and added. Pressurized nitrogen replacement (0.2 MPaG) was repeated three times. After stirring was started at 60°C, the temperature was raised to 230°C over 1 hour, and the reaction was carried out for 6 hours. The pressure when reaching the reaction temperature was 0.3 MPaG. After completion of the reaction, the reaction mixture was cooled to 80° C., returned to normal pressure (101.3 kPa), and the reactant was transferred to a 1 L four-necked flask. The temperature was raised to 180° C. with stirring, and the remaining internal olefin was distilled off at 1.3 kPa in 1 hour. Subsequently, after cooling to room temperature (25° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the target alkenyl succinic anhydride (a). The average molecular weight of alkenyl succinic anhydride (a) determined from the acid value was 337.

Production Examples b to e (production of alkenyl succinic anhydrides b to e)
Alkenyl succinic anhydrides b to e were obtained in the same manner as in Production Example a, except that the types and amounts of the raw materials, antioxidants, and polymerization inhibitors were changed as shown in Table 1. The average molecular weight of the alkenyl succinic anhydride was obtained from the acid value and shown in Table 1.

[Production of amorphous polyester resin]
Production Examples A1 to A5 (production of amorphous polyester resins A-1 to A-5)
The polyester raw material monomers other than trimellitic anhydride, the esterification catalyst and the esterification co-catalyst shown in Table 2 are placed in a 5 L four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple, and nitrogen Under the atmosphere, the temperature was raised to 235° C., and then polycondensation was carried out at 235° C. for 6 hours. After that, the temperature was lowered to 210° C., trimellitic anhydride was added, and the mixture was reacted at 210° C. for 1 hour. Thereafter, reaction was carried out at 210° C. under a reduced pressure of 10 kPa to the softening point shown in Table 2 to obtain amorphous polyester resins A-1 to A-5. Various physical properties were measured, and the physical properties are shown in Table 2.

Production Example A6 (Production of Amorphous Polyester Resin A-6)
The polyester starting monomers other than sebacic acid and trimellitic anhydride, the esterification catalyst and the esterification co-catalyst shown in Table 2 were added to a 5 L four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple. The temperature was raised to 235° C. under a nitrogen atmosphere, and then polycondensation was carried out at 235° C. for 6 hours. Then, the temperature was lowered to 180°C, sebacic acid and trimellitic anhydride were added, the temperature was raised to 210°C at a rate of 10°C/hour, and then the reaction was carried out at 210°C for 1 hour. Thereafter, reaction was carried out at 210° C. under a reduced pressure of 10 kPa to the softening point shown in Table 2 to obtain an amorphous polyester resin A-6. Various physical properties were measured, and the physical properties are shown in Table 2.

[Production of crystalline polyester resin]
Production Examples C1 to C5 (Production of crystalline polyester resins C-1 to C-5)
The raw material monomers shown in Table 3 are placed in a 5 L four-necked flask equipped with a thermometer, stainless steel stirring rod, flow-down condenser and nitrogen inlet tube, and heated to 200° C. in a nitrogen atmosphere in a mantle heater for 8 hours. The temperature was raised over a period of time. After that, an esterification catalyst was added and the reaction was carried out at 8.0 kPa until the softening point shown in Table 3 was reached to obtain crystalline polyester resins C-1 to C-5. Various physical properties were measured, and the physical properties are shown in Table 3.

Example 1 (Production of Toner 1)
100 parts by mass of binder resin (amorphous polyester resin A-1/crystalline polyester resin C-1 = 90/10 (mass ratio)), coloring agent "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) 5 Part by mass, 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of paraffin wax "HNP0190" (manufactured by Nippon Seiro Co., Ltd., melting point: 85 ° C.) as a release agent. After thoroughly stirring with a Henschel mixer, the mixture was melt-kneaded using a co-rotating twin-screw extruder having a kneading part with a total length of 1560 mm, a screw diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the screw was 200 r/min, the heating temperature inside the screw was 90°C, the temperature of the kneaded material was 140°C, the supply rate of the kneaded material was 10 kg/h, and the average residence time was about 18 seconds. The resulting kneaded product was cooled from 140° C. to 50° C. in 1.5 hours, rolled and cooled at 50° C. with a cooling roller, allowed to stand at 45° C. for 4 hours, pulverized with a jet mill, classified, and volumetrically Toner particles with a median particle size (D ₅₀ ) of 5.5 μm were obtained.

To 100 parts by mass of the obtained toner particles, 1.5 parts by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle diameter: 16 nm) is added as an external additive. , And hydrophobic silica "RY-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size: 40 nm) 1.0 parts by mass are added, and mixed with a Henschel mixer at 3600 r / min for 5 minutes. By doing so, external addition treatment was performed, and Toner 1 was obtained. Various evaluations were performed and the results are shown in Table 4.

Examples 2 to 7, Comparative Examples 1 to 4 (production of toners 2 to 7 and 81 to 84)
Toners 2 to 7 and 81 to 84 were obtained in the same manner as in Example 1, except that the resins A and C used as the binder resins were changed as shown in Table 4.

From the results of Examples and Comparative Examples, it can be seen that the toner of the present invention is excellent in low-temperature fixability, heat-resistant storage stability, and glossiness.

Claims (4)

containing an amorphous polyester resin and a crystalline polyester resin,
The amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms,
In the carboxylic acid component of the amorphous polyester resin, succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms and succinic acid substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms or The molar ratio of the anhydride is 30/70 or more and 70/30 or less ,
The toner for electrostatic charge image development, wherein the crystalline polyester resin is a polycondensate of an alcohol component containing an aliphatic diol having 4 to 6 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 carbon atoms. . 2. The toner for electrostatic charge image development according to claim 1, wherein the alcohol component in the crystalline polyester resin contains an aliphatic diol having 4 to 6 carbon atoms. The ratio of the succinic acid substituted with the linear aliphatic hydrocarbon group having 16 to 18 carbon atoms or the anhydride thereof is 1 mol part or more and 30 mol parts per 100 mol parts of the alcohol component of the amorphous polyester resin. 3. The toner for electrostatic charge image development according to claim 1, wherein the toner is less than or equal to 10 parts. The mass ratio of the amorphous polyester resin to the crystalline polyester resin [amorphous polyester resin/crystalline polyester resin] is 80/20 or more and 99/1 or less, according to any one of claims 1 to 3. toner for developing electrostatic charge images.