JP2016138988A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of making the fixation at a lower temperature and maintaining high transferability even in an image output of an extended period.SOLUTION: A toner cools a mixture having an admixture containing a crystalline polyester resin A, a resin composition B, a resin composition C, and a hydrocarbon wax after fused and kneaded, pulverizes the obtained kneaded material, thereby obtaining toner particles by subjecting the obtained pulverize material to heat treatment. The resin composition B is a hybrid resin obtained by chemically connecting the polyester resin component and the vinyl resin component. The resin component C is a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component. The melting point T1(°C) of the crystalline polyester resin A, the melting point T2(°C) of the hydrocarbon wax, and the transition temperature T3(°C) of the resin component C which are measured by a differential scanning calorimeter satisfy a specific relationship.SELECTED DRAWING: None

Description

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

In recent years, electrophotographic full-color copiers have become widespread and have started to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are demanded while supporting a wide range of media (paper types). For example, even when the paper type is changed from thick paper to thin paper, there is a demand for media speed that continues printing without changing the process speed according to the paper type or changing the fixing device heating set temperature.
From the viewpoint of media isovelocity, the toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature.
Various toners have been proposed in which a crystalline resin having sharp melt properties is added to the toner to improve the low-temperature fixing performance in order to fix the toner at a wide fixing temperature. Among them, a toner is proposed in which a resin dispersant obtained by grafting a non-linear crystalline polyester and a polyolefin resin with a vinyl resin is added to a hybrid resin (see Patent Document 1). However, high-speed machines corresponding to the printing market still lacked low-temperature fixability. Further, since the toner shape is not controlled, the transfer efficiency may be insufficient.
In order to achieve high image quality, it is necessary to increase the transfer efficiency from the electrostatic latent image carrier to the intermediate transfer member and the transfer efficiency from the intermediate transfer member to the paper. A proposal has been made to improve the transfer efficiency by controlling the shape by heat-treating the toner, lowering the adhesion of the toner, and transferring efficiency (see Patent Document 2).
However, it is known that the heat-treated toner controls the shape of the toner, while the highly adhesive wax elutes near the toner surface. For this reason, the transfer efficiency deteriorates due to the influence of the wax eluted near the toner surface. As a result, when paper with low surface smoothness such as embossed paper or rough paper is used, toner may not be transferred from the intermediate transfer body in areas where sufficient transfer pressure is not applied, and image quality defects called white spots may occur. is there.
As described above, there is still room for study in order to enable fixing at a lower temperature and maintain high transferability even in long-term image output.

JP 2007-293327 A JP 2011-123352 A

  The present invention provides a toner capable of fixing at a lower temperature and maintaining high transferability even for long-term image output.

As a result of intensive studies, the present inventors have found the following to reach the present invention in order to enable fixing at a lower temperature and maintain high transferability even in long-term image output.
That is, the present invention is to cool a mixture containing crystalline polyester resin A, resin composition B, resin composition C, and hydrocarbon wax after melt-kneading, pulverize the obtained kneaded product, and obtain the pulverized product A toner having toner particles obtained by heat-treating an object,
(1) The resin composition B is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component,
(2) The resin composition C is a polymer obtained by reacting the hydrocarbon compound and a vinyl resin component,
(3) The melting point of the crystalline polyester resin A measured by a differential scanning calorimeter (DSC) is T1 (° C.), the melting point of the hydrocarbon wax is T2 (° C.), and the glass transition temperature of the resin composition C. And T3 (° C.), the toner satisfies the following relationship.
| T3-T1 | ≦ 15 (Formula 1)
| T2-T1 | ≦ 15 (Formula 2)
60 ° C. ≦ T1 ≦ 85 ° C. (Formula 3)

  According to the present invention, it is possible to provide a toner that can be fixed at a lower temperature and can maintain high transferability even during long-term image output.

Diagram of heat treatment equipment used in the present invention

In the toner of the present invention, the mixture containing the crystalline polyester resin A, the resin composition B, the resin composition C, and the hydrocarbon wax is cooled after melt kneading, the obtained kneaded material is pulverized, and the obtained pulverization is performed. A toner having toner particles obtained by heat-treating an object,
(1) The resin composition B is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component,
(2) The resin composition C is a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component,
(3) The melting point of the crystalline polyester resin A measured by a differential scanning calorimeter (DSC) is T1 (° C.), the melting point of the hydrocarbon wax is T2 (° C.), and the glass transition temperature of the resin composition C. Is T3 (° C.), the following relationship is satisfied.
| T3-T1 | ≦ 15 (Formula 1)
| T2-T1 | ≦ 15 (Formula 2)
60 ° C. ≦ T1 ≦ 85 ° C. (Formula 3)

The toner of the present invention includes a crystalline polyester resin A, a resin composition C, and a hydrocarbon wax that satisfy the relationships of the above (formula 1) to (formula 3), and a resin composition B as a main binder resin. And a toner particle obtained by heat-treating the obtained pulverized product.
By using the toner, fixing at a lower temperature is possible. Further, by suppressing wax elution on the toner surface, high transferability is maintained even during long-term image output.
In the present invention, by adding the crystalline polyester resin A to the resin composition B, fixing at a lower temperature becomes possible. The reason is guessed as follows.
The resin composition B is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component.
Since the vinyl resin component of the resin composition B functions as a dispersion aid for the crystalline polyester resin A, the crystalline polyester resin A crystals can be finely dispersed in the toner in the cooling step after melt-kneading. As a result, variations in melting characteristics between toner particles are reduced, the response speed to the temperature applied at the time of fixing is high, and variations in the response speed are reduced.
For example, when the crystalline polyester resin A is added to a normal polyester resin, the effect of dispersing the vinyl resin component on the crystalline polyester resin A cannot be obtained. Therefore, the dispersion diameter of the crystalline polyester resin A becomes relatively large, and the above effect cannot be obtained. Further, since the dispersion diameter of the crystalline polyester resin A becomes large, the exposed area of the crystalline polyester resin A at the pulverization interface tends to be large, and when left in a high-humidity environment, the charge amount is greatly reduced and fogging is caused. It may cause image damage.

On the other hand, it is presumed that the high transferability is maintained even during long-term image output as described above because the elution of hydrocarbon wax near the toner surface is effectively suppressed.
In a normal toner in which hydrocarbon wax is dispersed alone, the wax is eluted near the toner surface by heat treatment. As a result, toner adhesion increases and transfer efficiency decreases.
On the other hand, in the toner of the present invention, the hydrocarbon wax is held inside the toner, and even if heat treatment is performed, the wax does not elute to the toner surface. As a result, high transferability is maintained even during long-term image output.
This effect is presumed to be caused by a specific combination of the constituent materials of the toner of the present invention.
First, in the present invention, since the vinyl resin component of the resin composition B and the crystalline polyester resin A are close in polarity, in the cooling process after melt kneading, the vinyl resin component and the crystalline polyester resin A are in the state of being close to each other in the toner. It is thought that it is fixed to.
The resin composition C is also a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component. Similarly to the resin composition B, the vinyl resin component of the resin composition C and the crystalline polyester resin A It is thought to be fixed at a close position.
In the toner of the present invention in which the resin compositions B and C and the crystalline polyester resin A are cooled after being melt-kneaded, the vinyl resin component of the resin compositions B and C is fixed with the crystalline polyester resin A interposed therebetween. Conceivable.
Furthermore, the resin composition C is a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component. The hydrocarbon compound and the hydrocarbon wax are easily compatible with each other in terms of polarity and structure. It also functions as a wax dispersant. Therefore, it is considered that finely dispersed hydrocarbon wax exists in the vicinity of the hydrocarbon compound of the resin composition C.
As described above, the vinyl resin component of the resin composition B serving as the binder resin and the crystalline polyester resin A are close to each other. And the vinyl resin component of the resin composition C approaches through the finely dispersed crystalline polyester resin A. Further, it is considered that the hydrocarbon wax finely dispersed through the hydrocarbon compound of the resin composition C is close to each other and is present at a position where the respective components are connected.
That is, the toner of the present invention has a continuous component arrangement from the vinyl resin component of the resin composition B to the crystalline polyester resin A and further from the resin composition C to the finely dispersed hydrocarbon wax.
In other words, the toner of the present invention is considered to be fixed in the toner in a state where the resin composition B-crystalline polyester resin A-resin composition C-hydrocarbon wax is combined.
By taking this composite state, the hydrocarbon wax is held in the toner while being finely dispersed in the toner, and even if heat treatment is performed, it does not elute to the vicinity of the toner surface, thereby preventing a decrease in transferability. thinking.

In the toner of the present invention, in order to fix the resin composition B-crystalline polyester resin A-resin composition C-hydrocarbon wax in a composite state in the toner, each component is specified as above. It is necessary to satisfy the relationships (Formula 1) to (Formula 3).
When each component satisfies the above-mentioned specific relationship, in the cooling step after melt-kneading the mixture containing the crystalline polyester resin A, the resin composition B, the resin composition C, and the hydrocarbon wax, Solidify at the same time. As a result, it is presumed that each component is fixed in the toner in a compounded state.
In order for each component to solidify at the same time, the absolute value of the difference between the glass transition temperature [T3 (° C.)] of the resin composition C and the melting point [T1 (° C.)] of the crystalline polyester resin A is 15 ° C. or less. That is, it is important to satisfy (Equation 1).
When the absolute value of the difference between T3 and T1 is 15 ° C. or less, the crystalline polyester resin A and the resin composition C can be solidified at the same time. As a result, the resin composition C forms a composite state via the crystalline polyester resin A, and the resin composition C is held. As a result, even if heat treatment is performed, elution of the hydrocarbon wax together with the resin composition C as a wax dispersant to the vicinity of the toner surface can be suppressed.
When the absolute value of the difference between T3 and T1 exceeds 15 ° C., there is no timing to solidify the crystalline polyester resin A and the resin composition C, and the resin composition C has a composite state through the crystalline polyester resin A. It is difficult to take. As a result, it is considered that the retention effect on the hydrocarbon wax does not appear, and the hydrocarbon wax is eluted together with the resin composition C to the vicinity of the toner surface by heat treatment. As a result, the transfer efficiency decreases.
The absolute value of the difference between T3 and T1 is preferably 0 or more and 12 or less, and more preferably 0 or more and 10 or less.

Similarly, the absolute value of the difference between the melting point [T1 (° C.)] of the crystalline polyester resin A and the melting point [T2 (° C.)] of the hydrocarbon wax is 15 ° C. or less, that is, satisfies (Equation 2). is important.
Similarly, when the absolute value of the difference between T2 and T1 is 15 ° C. or less, the crystalline polyester resin A and the hydrocarbon wax can be solidified at the same time. As a result, the hydrocarbon wax forms a composite state through the crystalline polyester resin A. As a result, the hydrocarbon wax takes a composite state with the resin composition C through the crystalline polyester resin A at the same time, and is fixed in the toner particles. It is thought that elution into the can be suppressed.
The absolute value of the difference between T2 and T1 is preferably 0 or more and 10 or less, and more preferably 0 or more and 8 or less.

The melting point [T1 (° C.)] of the crystalline polyester resin A of the present invention is 60 ° C. or higher and 85 ° C. or lower. When the melting point is 60 ° C. or higher and 85 ° C. or lower, the toner particles can be plasticized even in a high-speed fixing process, and the toner can be fixed at a low temperature.
In the present invention, the crystalline resin means a resin having a clear endothermic peak (that is, a melting point), not a stepwise endothermic amount change, as measured by a differential scanning calorimeter (DSC).
When T1 is less than 60 ° C., not only the storage stability of the toner is deteriorated, but also when an image with a low image ratio is continuously output in a high-temperature and high-humidity environment, embedding of external additives occurs and the development May decrease.
If T1 exceeds 85 ° C., the toner cannot be sufficiently plasticized at the time of fixing, and fixing at a low temperature becomes difficult.
The melting point of the crystalline polyester resin A is preferably 65 ° C. or higher and 80 ° C. or lower, and more preferably 70 ° C. or higher and 80 ° C. or lower.
From the above, in order to solidify the above components at the same timing, it is important to set the range of (Expression 1) to (Expression 3).
In addition, the melting point of the crystalline polyester resin A, the melting point of the hydrocarbon wax, and the glass transition temperature of the resin composition C can be easily adjusted by appropriately selecting each component.

Hereinafter, a preferable toner configuration in the present invention will be described in detail.
<Crystalline polyester resin A>
The crystalline polyester resin A of the present invention comprises an alcohol component containing at least one compound selected from the group consisting of aliphatic diols having 2 to 22 carbon atoms and derivatives thereof, and 2 to 22 carbon atoms. It is obtained by polycondensation with a carboxylic acid component containing at least one compound selected from the group consisting of aliphatic dicarboxylic acids and derivatives thereof.
Among them, it contains at least one compound selected from the group consisting of aliphatic diols having 6 to 12 carbon atoms and derivatives thereof from the viewpoint of achieving both low-temperature fixability and storage stability at a higher level. A crystalline polyester resin obtained by polycondensation of an alcohol component and a carboxylic acid component containing at least one compound selected from the group consisting of aliphatic dicarboxylic acids having 6 to 12 carbon atoms and derivatives thereof A is preferred.
The aliphatic diol having 2 to 22 carbon atoms (preferably 6 to 12 carbon atoms) is not particularly limited, but may be a linear (preferably linear) aliphatic diol.
For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, and Neopentyl glycol is mentioned. As well as their derivatives. The derivative is not particularly limited as long as a similar resin structure can be obtained by the above condensation polymerization. For example, the derivative which esterified the said diol is mentioned.
Among these, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12 -Dodecanediol etc. are illustrated preferably.
In the alcohol component, at least one compound selected from the group consisting of aliphatic diols having 2 to 22 carbon atoms and derivatives thereof is preferably 50% by mass or more based on the total alcohol components, It is more preferable that it is 70 mass% or more.
Furthermore, in the alcohol component, at least one compound selected from the group consisting of aliphatic diols having 6 to 12 carbon atoms and derivatives thereof is 50% by mass or more based on the total alcohol components. Is more preferable, and 70% by mass or more is particularly preferable.

In the present invention, a polyhydric alcohol can be used in addition to the aliphatic diol.
Among the polyhydric alcohols, diols other than the above aliphatic diols include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like.
Among the polyhydric alcohols, trihydric or higher polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4 -Aliphatic alcohols such as butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane It is done.
Furthermore, in this invention, you may use a monovalent alcohol to such an extent that the characteristic of the crystalline polyester resin A is not impaired. Examples of the monovalent alcohol include monovalent alcohols such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, and benzyl alcohol. .

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (preferably 6 to 12 carbon atoms) is not particularly limited, but may be a linear (preferably linear) aliphatic dicarboxylic acid.
For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid , Fumaric acid, mesaconic acid, citraconic acid, and itaconic acid. As well as their derivatives. The derivative is not particularly limited as long as a similar resin structure can be obtained by the above condensation polymerization.
Examples thereof include acid anhydrides of the above dicarboxylic acid components and derivatives obtained by methyl esterification, ethyl esterification, or acid chloride conversion of the dicarboxylic acid component.
In the present invention, in the carboxylic acid component, at least one compound selected from the group consisting of aliphatic dicarboxylic acids having 2 to 22 carbon atoms and derivatives thereof is 50% by mass or more based on the total carboxylic acid component. It is preferable that it is 70 mass% or more.
Furthermore, in the carboxylic acid component, at least one compound selected from the group consisting of aliphatic dicarboxylic acids having 6 to 12 carbon atoms and derivatives thereof is 50% by mass or more based on the total carboxylic acid component. It is more preferable that it is 70 mass% or more.

In the present invention, a polyvalent carboxylic acid can be used in addition to the aliphatic dicarboxylic acid.
Among the polyvalent carboxylic acids, divalent carboxylic acids other than the aliphatic dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid. An alicyclic carboxylic acid such as cyclohexanedicarboxylic acid, and these acid anhydrides or lower alkyl esters are also included.
In addition, as other polyvalent carboxylic acids, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2, Aromatic carboxylic acids such as 4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2 -Aliphatic carboxylic acids such as methylene carboxypropane, and derivatives of these acid anhydrides or lower alkyl esters are also included.
Furthermore, in this invention, you may contain monovalent carboxylic acid to such an extent that the characteristic of the crystalline polyester resin A is not impaired. Examples of the monovalent carboxylic acid include 1 such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, and octanoic acid. Valent carboxylic acid.

Furthermore, the crystalline polyester resin A of the present invention comprises an aliphatic monocarboxylic acid having 10 to 20 carbon atoms (preferably having 12 to 18 carbon atoms) and 10 to 20 carbon atoms at the terminal of the crystalline polyester resin A. One or more aliphatic compounds selected from the group consisting of aliphatic monoalcohols (preferably having 13 to 18 carbon atoms) (hereinafter these two are collectively referred to as “long-chain aliphatic compounds”) A resin bonded by condensation is preferable.
Specifically, when a carboxyl group is present at the terminal of the crystalline polyester resin A before the long-chain aliphatic compound is bonded, a condensation reaction with a monoalcohol occurs to generate a bond. Further, when a hydroxy group is present at the terminal of the crystalline polyester resin A before the long-chain aliphatic compound is bonded, a condensation reaction with a monocarboxylic acid occurs and a bond is generated.
Here, the term “terminal” includes, if the crystalline polyester resin A has a branched chain, the terminal of the branched chain.
In the crystalline polyester resin A of the present invention, the long-chain aliphatic compound is bonded to the terminal of the crystalline polyester resin A, so that the storage stability of the toner is improved.
From this fact, it is considered that the long-chain aliphatic compound is bonded to the terminal, whereby the crystallization speed of the crystalline polyester resin A is increased, and is fixed in a more finely dispersed state in the cooling step after melt-kneading. .
In general, the crystalline part is supposed to grow after the formation of crystal nuclei. In the present invention, by having a long chain aliphatic compound at the terminal of the crystalline polyester resin A, the hydrocarbon of the terminal long chain aliphatic compound can take a crystal structure of the crystalline polyester resin A (hereinafter, It is considered that the crystal growth can be promoted to the portion a) and the crystallization speed of the crystalline polyester resin A can be improved.
In addition, the affinity between the crystalline polyester resin A and the vinyl resin component of the resin composition B or the vinyl resin component of the resin composition C can be appropriately adjusted. This facilitates continuous component arrangement from the polyester resin A and the resin composition C to the finely dispersed hydrocarbon wax.
The compound that forms the long-chain aliphatic compound is not particularly limited as long as it is a compound having a crystallization rate faster than that of the site a. However, from the viewpoint of high crystallization speed, the main chain is preferably a compound containing one or more functional groups capable of reacting with the terminal of the crystalline polyester resin A, including a hydrocarbon-based portion. Furthermore, a compound in which the hydrocarbon moiety is linear and the number of functional groups that react with the crystalline polyester resin A is one is preferable.
Further, from the viewpoint of increasing the reactivity between the long chain aliphatic compound and the terminal of the crystalline polyester resin A, the molecular weight of the long chain aliphatic compound is preferably 100 or more and 10,000 or less, and 150 or more and 5,000 or less. It is more preferable that
From the viewpoint of increasing the crystallization speed, the long-chain aliphatic compound is contained in the crystalline polyester resin A in an amount of 0.1 mol part or more to 100 mol parts of the raw material monomer of the polyester molecular chain of the crystalline polyester resin A. It is preferably 0.0 mol part or less, more preferably 0.2 mol part or more and 7.0 mol part or less.
Within the above range, the affinity between the crystalline polyester resin A and the vinyl resin component of the resin composition B or the vinyl resin component of the resin composition C can be appropriately adjusted. This makes it easier to arrange the continuous components from the vinyl resin component to the crystalline polyester resin A and further from the resin composition C to the finely dispersed hydrocarbon wax.

Examples of the aliphatic monocarboxylic acid having 10 to 20 carbon atoms include the following.
Capric acid (decanoic acid), undecyl acid, lauric acid (dodecanoic acid), tridecyl acid, myristic acid (tetradecanoic acid), pentadecylic acid, palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid) , Nonadecyl acid, and arachidic acid (icosanoic acid).
Examples of the aliphatic monoalcohol having 10 to 20 carbon atoms include the following.
Decyl alcohol (decanol), undecanol, lauryl alcohol (dodecanol), tridecanol, myristyl alcohol (tetradecanol), pentadecanol, palmityl alcohol (hexadecanol), heptadecanol, stearyl alcohol (octadecanol), nonadecanol And arachidyl alcohol (icosanol).
Whether or not the long-chain aliphatic compound is bonded to the crystalline polyester resin A is determined by the following analysis.
2 mg of the sample is precisely weighed, and 2 ml of chloroform is added and dissolved to prepare a sample solution. Crystalline polyester resin A is used as the resin sample. However, if it is difficult to obtain crystalline polyester resin A, a toner containing crystalline polyester resin A can be used as a sample.
Next, 20 mg of 2,5-dihydroxybenzoic acid (DHBA) is precisely weighed, and 1 ml of chloroform is added and dissolved to prepare a matrix solution.
In addition, after accurately weighing 3 mg of sodium trifluoroacetate (NaTFA), 1 ml of acetone is added and dissolved to prepare an ionization aid solution.
The sample solution thus prepared (25 μl), the matrix solution (50 μl), and the ionization aid solution (5 μl) are mixed, dropped onto a sample plate for MALDI analysis, and dried to obtain a measurement sample.
As an analytical instrument, MALDI-TOFMS (R made by Bruker Daltonics)
mass spectrum is obtained using eflex III).
In the obtained mass spectrum, each peak in the oligomer region (m / Z is 2000 or less) is assigned, and it is confirmed whether or not there is a peak corresponding to the composition in which the long chain aliphatic compound is bonded to the molecular end. .

In the present invention, the content of the crystalline polyester resin A contained in the toner particles is preferably 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin composition B. It is more preferable that the amount is not more than part by mass.
When the content of the crystalline polyester resin A is in the above-mentioned range, sufficient low-temperature fixability is exhibited and the crystalline polyester resin A can be finely dispersed in the toner, which is more preferable.
In the present invention, the content of the crystalline polyester resin A contained in the toner particles is more preferably equal to or more than the content of the resin composition C, and relative to 100 parts by mass of the resin composition C. 120 parts by mass or more and 200 parts by mass or less is more preferable.
When the content of the crystalline polyester resin A is equal to or more than the content of the resin composition C, the crystalline polyester resin A and the resin composition C can be fixed at close positions, and during heat treatment The effect of suppressing the elution of the wax is sufficiently exhibited.

In the present invention, the crystalline polyester resin A can be produced according to an ordinary polyester synthesis method. For example, the above-described carboxylic acid component and alcohol component are esterified or transesterified, and then subjected to a condensation polymerization reaction under reduced pressure or by introducing nitrogen gas in accordance with a conventional method to obtain a desired crystalline polyester resin. Can be obtained.
The above esterification or transesterification reaction is carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, tin (II) octylate, dibutyltin oxide, manganese acetate, and magnesium acetate as necessary. It can be carried out.
In addition, the above condensation polymerization reaction may be carried out using conventional polymerization catalysts such as titanium butoxide, tin (II) octylate, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. Can be done using. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.
In the esterification or transesterification reaction, or the condensation polymerization reaction, all monomers are charged at once to increase the strength of the resulting crystalline polyester resin, and divalent monomers are used to reduce low molecular weight components. First, after reacting, a method such as adding a trivalent or higher monomer to react may be used.

<Resin composition B (binder resin)>
In the present invention, the toner particles contain the resin composition B as a binder resin.
The resin composition B is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component.
In the present invention, the binder resin can use the resin composition B (hybrid resin) alone, but may be a mixture containing other resins as the binder resin.
For example, a mixture of a hybrid resin and a vinyl resin, a mixture of a hybrid resin and a polyester resin, a mixture of a polyester resin, a hybrid resin, and a vinyl resin, or the like can be given.
Examples of the hybrid resin include the following.
(I) What is formed by performing a transesterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid ester group such as an acrylic ester or a methacrylic ester and a polyester resin component.
(Ii) Those formed by causing an esterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid and a polyester resin component.
(Iii) What is formed by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin component polymerized using a monomer having an unsaturated bond such as fumaric acid.
The hybrid resin is obtained by containing a monomer component capable of reacting with both resin components in the vinyl resin component and / or the polyester resin component as described in (i) or (ii) above and reacting them. be able to.
Among the monomers constituting the polyester resin component, those capable of reacting with the vinyl resin component include, for example, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof.
Among the monomers constituting the vinyl resin component, those that can react with the polyester resin component include vinyl monomers having a carboxyl group such as acrylic acid and methacrylic acid, and vinyl monomers having a hydroxy group.
In the present invention, from the viewpoint of finely dispersing the crystalline polyester resin A and fixing the crystalline polyester resin A and the vinyl resin component of the resin composition B close to each other, the vinyl of the polyester resin component in the resin composition B The mass ratio to the resin component is preferably 50:50 to 95: 5, and more preferably 70:30 to 90:10.

As a manufacturing method of the said hybrid resin, the manufacturing method shown to the following (1)-(5) can be mentioned, for example.
(1) After separately producing a vinyl resin and a polyester resin, the polyester resin component and the vinyl resin are dissolved or swollen in a small amount of an organic solvent, an esterification catalyst and an alcohol are added, and the ester exchange reaction is performed by heating. A hybrid resin having components is obtained.
(2) After the vinyl resin is produced, a polyester resin component is produced in the presence of the vinyl resin, and a hybrid resin having the polyester resin component and the vinyl resin component is produced. Also in this case, an organic solvent can be appropriately used.
(3) After the production of the polyester resin, a vinyl resin component is produced in the presence of the polyester resin and reacted to produce a hybrid resin having the polyester resin component and the vinyl resin component.
(4) After the vinyl resin and the polyester resin are produced, a hybrid resin is produced by adding a vinyl monomer and / or a polyester monomer (alcohol component, carboxylic acid component) in the presence of these polymer components. Also in this case, an organic solvent can be appropriately used.
(5) A hybrid resin having a polyester resin component and a vinyl resin component is produced by mixing a vinyl monomer and a polyester monomer (alcohol component, carboxylic acid component) and continuously performing an addition polymerization and a condensation polymerization reaction. Furthermore, an organic solvent can be used as appropriate.
In the production methods (1) to (5) above, the vinyl resin component and / or the polyester resin component can use polymer components having a plurality of different molecular weights and degrees of crosslinking.
The hybrid resin preferably has a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 1.0 or more and 5.0 or less from the viewpoint of sharp melt property at the time of fixing. More preferably, it is 1.0 or more and 3.0 or less.
The hybrid resin preferably has an acid value of 0.1 mgKOH / g or more and 30 mgKOH / g or less, more preferably 1 mgKOH / g or more and 20 mgKOH / g or less, from the viewpoint of imparting good chargeability to the toner. More preferably, it is 1 mgKOH / g or more and 10 mgKOH / g or less.
Further, the hybrid resin preferably has a hydroxyl value of 10 mgKOH / g or more and 60 mgKOH / g or less, more preferably 20 mgKOH / g or more and 60 mgKOH / g or less, from the viewpoint of imparting good chargeability to the toner. More preferably, they are 30 mgKOH / g or more and 50 mgKOH / g or less.

The polyester resin component and vinyl resin component constituting the hybrid resin will be described.
The monomer which can be used when manufacturing a polyester resin component is illustrated below.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol represented by the following formula (A) and derivatives thereof, and diols represented by the following formula (B).

Examples of the divalent carboxylic acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, anhydrides thereof, or lower alkyl esters thereof; succinic acid, adipic acid, sebacic acid, azelaic acid Dicarboxylic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, alkenyl succinic acids or alkyl succinic acids, anhydrides thereof, or lower alkyl esters thereof; And derivatives thereof.
Moreover, it is made into unsaturated polyester resin by containing unsaturated dicarboxylic acids, such as fumaric acid, maleic acid, citraconic acid, itaconic acid, and n-dodecenyl succinic acid, its anhydride, or its lower alkyl ester as a structural component. It is also possible.
The content of these unsaturated dicarboxylic acids is preferably 0.1 mol% or more and 10 mol% or less, more preferably 0.3 mol% or more and 5 mol% or less, based on the total carboxylic acid component of the polyester monomer, Preferably they are 0.5 mol% or more and 3 mol% or less.
When the unsaturated dicarboxylic acid content is in the above range, the unsaturated bond concentration in the molecule of the polyester resin component is appropriate, and the polyester resin and vinyl resin having an appropriate distance between the crosslinking points are hybridized. Is preferable from the viewpoint of improving the dispersibility of the crystalline polyester resin A.

Moreover, in the said polyester resin component, it is also possible to use a trivalent or more alcohol component and a trivalent or more carboxylic acid component as needed.
Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-
Examples include butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxybenzene.
On the other hand, examples of the trivalent or higher carboxylic acid component include pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) Examples include methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, tetracarboxylic acid represented by the following formula (C), anhydrides thereof, and lower alkyl esters thereof.

（式Ｃ中、Ｘは炭素数３以上の側鎖を１個以上有する、炭素数５以上３０以下のアルキレン基又は炭素数５以上３０以下のアルケニレン基を表す。）

(In Formula C, X represents an alkylene group having 5 or more and 30 or less carbon atoms or an alkenylene group having 5 or more and 30 or less carbon atoms and having one or more side chains having 3 or more carbon atoms.)

Among these, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, their anhydrides, and lower alkyl esters thereof are preferable.
In the polyester resin component, the alcohol component is 40 mol% to 60 mol% (more preferably 45 mol% to 55 mol%) and the carboxylic acid component is 60 mol% to 40 mol% (more preferably) with respect to all components. 55 mol% or more and 45 mol% or less) is preferable.
The trivalent or higher polyvalent component is preferably from 0.1 mol% to 60 mol%, more preferably from 0.1 mol% to 20 mol%, based on all components.

The polyester resin is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin is usually performed in the presence of a catalyst at a temperature of 150 ° C. or higher and 300 ° C. or lower, preferably 170 ° C. or higher and 280 ° C. or lower. The reaction can be performed under normal pressure, reduced pressure, or increased pressure, but after reaching a predetermined reaction rate (for example, about 30% to 90%), the reaction system is 200 mmHg or less, preferably 25 mmHg or less, The reaction is preferably carried out under a reduced pressure of 10 mmHg or less.
The catalyst used for the above polycondensation reaction is usually a catalyst used for polyester production, for example, metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and these metal-containing compounds. (Dibutyltin oxide, tin (II) dioctanoate, orthodibutyl titanate, tetrabutyl titanate, tetraisopropyl titanate, dipotassium oxalate titanate, potassium terephthalate titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, trioxide Antimony).
In the present invention, a titanium compound is preferably used because of easy control of the condensation polymerization reaction and high reactivity with a vinyl monomer, and tetraisopropyl titanate, dipotassium oxalate titanate, titanium terephthalate are particularly preferable. Examples include potassium acid. At this time, it is particularly preferable to add an antioxidant (particularly a phosphorus-based antioxidant) as an anti-coloring agent for the binder resin and a co-catalyst (a magnesium compound is preferable, and magnesium acetate is particularly preferable) as a reaction accelerator.
By stopping the reaction when the properties of the reactants (for example, acid value, softening point, etc.) reach a predetermined value, or when the stirring torque or stirring power of the reactor reaches a predetermined value, Can be obtained.

The vinyl resin is a vinyl homopolymer or a vinyl copolymer.
The following are mentioned as a monomer for obtaining a vinyl resin.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, and pn-dodecyl Styrene derivatives such as styrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; halogenated such as vinyl chloride, vinyl bromide and vinyl fluoride Vinyls; vinyls such as vinyl acetate, vinyl propionate, and vinyl benzoate Esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate Acrylic esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; vinyl methyl ether Vinyl ethers such as vinyl, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, And N-vinyl compounds such as N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.
These vinyl monomers may be used alone or as a mixture of two or more monomers.
Among these, a combination of monomers that becomes a styrene copolymer or a styrene acrylic copolymer is preferable.

Furthermore, as a monomer for adjusting the acid value of the binder resin, for example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, and crotonic acid, and α- or β-alkyl derivatives thereof; fumaric acid, malein Examples thereof include acids and unsaturated dicarboxylic acids such as citraconic acid and monoester derivatives or acid anhydrides thereof.
A desired binder resin can be produced by such monomers alone or in combination or copolymerized with other monomers.
Among these, the acid value may be controlled by using a monoester derivative of unsaturated dicarboxylic acid.
More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters of α, β-unsaturated dicarboxylic acids such as: monobutyl n-butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenylmalonate, monomethyl n-dodecenyl glutarate, monobutyl n-butenyl adipate Monoesters of alkenyl dicarboxylic acids such as, and the like; monoesters of aromatic dicarboxylic acids such as phthalic acid monomethyl ester, phthalic acid monoethyl ester, phthalic acid monobutyl ester, and the like.
The content of the carboxyl group-containing monomer as described above may be 0.1% by mass or more and 30% by mass or less with respect to all monomers used when the vinyl resin is synthesized.

It is also possible to add a crosslinkable monomer as exemplified below.
As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di) Acrylate, 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, and neopentyl glycol diacrylate, and acrylates of these compounds in place of methacrylate); linked by an alkyl chain containing an ether bond Diacrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, poly Tylene glycol # 600 diacrylate and dipropylene glycol diacrylate, and acrylates of these compounds in place of methacrylate); diacrylate compounds linked by chains containing aromatic groups and ether linkages (eg, poly Oxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and compounds of these Examples thereof include those obtained by replacing acrylate with methacrylate); polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)).
Examples of the polyfunctional crosslinking agent include pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of these compounds. Examples thereof include triallyl cyanurate and triallyl trimellitate.
The content of these crosslinking agents is preferably 0.001 to 1 part by mass, more preferably 0.001 to 0.05 part by mass, relative to 100 parts by mass of the vinyl monomer component. It is.

For the production of the vinyl resin, the following polymerization initiator may be used.
Examples of polymerization initiators include benzoyl peroxide, n-butyl-4,4-di (tert-butylperoxy) valerate, dicumyl peroxide, α, α′-bis (tert-butylperoxydiisopropyl) benzene, Examples thereof include organic peroxides such as tert-butyl peroxycumene and di-tert-butyl peroxide, azo and diazo compounds such as azobisisobutyronitrile, and diazoaminoazobenzene.

In the present invention, the resin composition B preferably contains 10% by mass or more and 30% by mass or less of a tetrahydrofuran-insoluble component in order to improve toner consumption, developability, and hot offset property.
Moreover, it is preferable that the glass transition temperature (Tg) of the resin composition B is 50 degreeC or more and 75 degrees C or less. By adjusting the glass transition temperature of the resin composition B to the above range, the storage stability of the toner and the fixing property of the toner can be further improved.

<Resin composition C>
In the present invention, the resin composition C contains a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component.
Examples of the polymer obtained by reacting the hydrocarbon compound and the vinyl resin component include a polymer obtained by graft copolymerization of a polyolefin with a vinyl resin component, or a polymer obtained by graft copolymerization of a vinyl monomer with a polyolefin. Is mentioned.
Here, polyolefin is a general term for polymers synthesized using a hydrocarbon compound having a double bond (C = C) or an alkene as a monomer.
The polymer obtained by reacting the hydrocarbon compound with the vinyl resin component has an effect of increasing the affinity between the melted resin composition B and the hydrocarbon wax in the melt-kneading step at the time of toner production. thinking. Therefore, it is preferable to add the polymer to the toner particles because the dispersibility of the hydrocarbon wax in the toner particles can be controlled. When the above polymer is not used, the cleaning property is deteriorated because the dispersion state of the hydrocarbon wax in the toner particles is insufficient.
As described above, the hydrocarbon compound is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon monomer having one double bond, and various polyolefins can be used.
In particular, polyethylene or polypropylene is preferably used.
On the other hand, the following are mentioned as a vinyl monomer used for the said vinyl resin component.
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene monomers such as styrene and its derivatives.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;
Vinyl monomers containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid.
Unsaturated dibasic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, and alkenyl succinic anhydride.
Maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumarate Half esters of unsaturated dibasic acids such as acid methyl half esters and mesaconic acid methyl half esters.
Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid.
Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid.
.Alpha.,. Beta.-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride.
An anhydride of the α, β-unsaturated acid and a lower fatty acid.
Vinyl monomers containing carboxyl groups such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and monoesters thereof.
Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate;
Vinyl monomers containing a hydroxyl group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.
Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- Vinyl ester monomers comprising acrylate esters such as chloroethyl and acrylate esters such as phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-n-octyl, methacrylate-decyl, methacrylate-2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacryl Vinyl ester monomers comprising methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid and diethylaminoethyl methacrylate.

The polymer obtained by reacting the hydrocarbon compound with the vinyl resin component is obtained by a known method such as a reaction between the vinyl monomers or a reaction between the monomer of one polymer and the other polymer. Can do.
The monomer unit constituting the vinyl resin component preferably includes a styrene monomer unit, a vinyl ester monomer unit, an acrylonitrile monomer unit, or a methacrylonitrile monomer unit.
Further, the glass transition temperature (Tg) of the polymer is preferably 50 ° C. or higher and 100 ° C. or lower in order to achieve both storage stability, low-temperature fixability, and hot offset property.
Furthermore, when the toner particles are obtained by heat treatment, coalescence of the toner particles becomes a problem, but is a rare material that prevents coalescence.
In the present invention, the mass ratio of the hydrocarbon compound to the vinyl resin component in the resin composition C is preferably 1:99 to 75:25. More preferably, it is 10: 90-70: 30.
Moreover, it is preferable that content of the resin composition C is less than the content of the crystalline polyester resin A, when maintaining the above-mentioned composite state.
On the other hand, the content of the resin composition C is preferably 0.2 parts by mass or more and 40.0 parts by mass or less, and more preferably 1.0 part by mass or more with respect to 100 parts by mass of the resin composition B. 20.0 parts by mass or less.

<Hydrocarbon wax>
In the present invention, the hydrocarbon wax is close in polarity to the hydrocarbon compound constituting the resin composition C and is compatible with each other. Therefore, the hydrocarbon wax is also a hydrocarbon compound similar to the hydrocarbon compound constituting the resin composition C.
Examples of the hydrocarbon wax include a low molecular weight alkene polymer obtained by radical polymerization of alkene under high pressure or a Ziegler catalyst or metallocene catalyst under low pressure; an alkene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; Examples thereof include synthetic hydrocarbon waxes obtained from a distillation residue of hydrocarbons obtained from a synthesis gas containing carbon oxide and hydrogen by the age method, or obtained by hydrogenating them.
Furthermore, what carried out the fractionation of the hydrocarbon wax by the press perspiration method, the solvent method, the use of vacuum distillation or the fractional crystallization method is more preferably used.
The hydrocarbon as the base is synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintole method, hydrocol method (fluid catalyst bed) Compound)]; hydrocarbons with up to several hundred carbon atoms obtained by the age method (using a fixed catalyst bed) that can produce a large amount of waxy hydrocarbons; alkenes such as ethylene using Ziegler catalysts Hydrocarbons polymerized by the above are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of an alkene is also preferred from its molecular weight distribution. Paraffin wax is also preferably used.
Hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferred from the viewpoint of improving low-temperature fixability and hot offset property.
In the present invention, the hydrocarbon wax content is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin composition B.
Moreover, in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC), the peak temperature of the maximum endothermic peak of the hydrocarbon wax is preferably 45 ° C. or higher and 140 ° C. or lower. It is preferable that the peak temperature of the maximum endothermic peak is within the above range since both the storage stability of the toner and the hot offset property can be achieved.

<Colorant>
In the present invention, the toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black; those obtained by adjusting the color to black using the following yellow colorant, magenta colorant, and cyan colorant.
As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the magenta toner pigment include the following.
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following.
C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the cyan toner pigment include the following.
C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan toner dyes include C.I. I. There is Solvent Blue 70.
Examples of the yellow toner pigment include the following.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.
The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin composition B.

<Charge control agent>
In the present invention, the toner particles may contain a charge control agent.
As the charge control agent, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high charging speed of toner particles, and can stably maintain a constant charge amount is preferable.
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene.
Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.
The charge control agent may be added internally or externally to the toner particles.
The content of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin composition B.

<Inorganic fine particles>
The toner of the present invention can also be made by adding inorganic fine particles to toner particles.
The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive.
As the external additive, inorganic fine particles such as silica, titanium oxide, and aluminum oxide are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
On the other hand, as an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² / g or more and 400 m ² / g or less are preferable. The external additive for stabilizing the durability is preferably inorganic fine particles having a specific surface area of 10 m ² / g or more and 50 m ² / g or less.
In order to achieve both improvement in fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used in combination.
When inorganic fine particles are used as the external additive, the amount is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. In this case, the toner particles and the inorganic fine particles can be mixed using a known mixer such as a Henschel mixer.

<Developer>
Although the toner of the present invention can be used as a one-component developer, it is preferably mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility.
Moreover, it is also preferable in that a stable image can be obtained over a long period of time.
Examples of the magnetic carrier include iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth, alloy particles thereof; oxide particles thereof; ferrite A generally known material such as a magnetic material dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state can be used.
When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier and the toner is such that the toner concentration in the two-component developer is 2% by mass or more and 15% by mass or less. It is preferable that it is 4 mass% or more and 13 mass% or less.

<Toner production method>
Next, a toner manufacturing method will be described.
The toner of the present invention was obtained by cooling the mixture containing the crystalline polyester resin A, the resin composition B, the resin composition C, and the hydrocarbon wax after melt-kneading, and pulverizing the obtained kneaded product. It can be obtained by heat treating the pulverized product.
First, a predetermined amount of crystalline polyester resin A, resin composition B, resin composition C, hydrocarbon wax, and the like are weighed, mixed, and mixed (raw material mixing step).
As an example of an apparatus used in the raw material mixing step, there are a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Mitsui Mining Co., Ltd.).
Next, the mixed mixture is melt-kneaded to disperse the crystalline polyester resin A, the resin composition C, the hydrocarbon wax, and the like in the resin composition B (melt-kneading step). In the melt-kneading step, the kneaded product is heated to about 160 ° C., for example.
In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko Co., Ltd.), twin screw extruder (manufactured by Kay Sea Kay Co., Ltd.) ), Co-kneader (manufactured by Buss), and kneedex (manufactured by Mitsui Mining).
Further, the kneaded product obtained by melt-kneading is rolled with a two roll or the like and then cooled using a refrigerant such as water (for example, water at about 15 ° C.) (cooling step). Natural cooling may be performed without using a refrigerant.
From the viewpoint of fixing the resin composition B-crystalline polyester resin A-resin composition C-hydrocarbon wax in a composite state, the cooling may be, for example, about 35 ° C. or less.
Next, the cooled kneaded product is pulverized to a desired particle size in a pulverization step. In the pulverization process, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, and a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), turbo It may be finely pulverized with a mill (manufactured by Turbo Kogyo Co., Ltd.) or an air jet type fine pulverizer.
Thereafter, the obtained pulverized product is heat-treated (heat treatment step) to obtain toner particles.

The heat treatment step is preferably performed using hot air from the viewpoints of toner particle coalescence and shape uniformity in the heat treatment step.
Hereinafter, although the heat processing process using a hot air is demonstrated, it is not limited to this description at all.
For the heat treatment process using hot air, for example, a processing apparatus as shown in FIG. 1 can be used.
Specifically, the pulverized material supplied in a fixed amount by the raw material supply unit 1 is guided to the introduction pipe 3 installed on the vertical line of the raw material supply unit by the compressed gas adjusted by the compressed gas flow rate adjusting unit 2. A process in which the pulverized material that has passed through the introduction pipe 3 is uniformly dispersed by a conical projection-like member 4 provided at the center of the raw material supply means, and is guided to a radially extending eight-direction supply pipe 5 to perform heat treatment. Guided to chamber 6.
At this time, the flow of the pulverized material supplied to the processing chamber is regulated by the restriction means 9 for regulating the flow of the pulverized material provided in the processing chamber. For this reason, the pulverized material supplied to the processing chamber is heat-treated while turning in the processing chamber and then cooled.
Hot air for heat-treating the supplied pulverized material is supplied from the hot air supply means 7, and is introduced through the distribution member 12 by swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. Is done. As the structure, the turning member 13 for turning hot air has a plurality of blades, and the turning of hot air can be controlled by the number and angle of the blades.
The temperature of the hot air supplied into the processing chamber is preferably 100 ° C. or higher and 300 ° C. or lower, more preferably 140 ° C. or higher and 230 ° C. or lower, at the outlet of the hot air supply means 7. If the temperature at the outlet of the hot air supply means 7 is within the above range, the average circularity of the toner particles is within a desired range while preventing the toner particles from fusing and coalescing due to overheating of the pulverized product. The toner particles can be uniformly heat-treated so as to satisfy.
Further, the heat-treated toner particles subjected to the heat treatment are cooled by the cold air supplied from the cold air supply means 8. The temperature of the cold air supplied from the cold air supply means 8 is preferably −20 ° C. or higher and 30 ° C. or lower. If the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, preventing the heat-treated toner particles from fusing and coalescing without inhibiting the uniform heat treatment of the toner particles. Can do. The absolute moisture content of the cold air is preferably 0.5 g / ^{m 3} or more 15.0 g / ^{m 3} or less.
Next, the cooled heat-treated toner particles are recovered by the recovery means 10 at the lower end of the processing chamber. In addition, a blower (not shown) is provided at the tip of the collecting means, and is thereby configured to be sucked and conveyed.
Moreover, the powder particle supply port 14 is provided so that the swirl direction of the supplied pulverized material and the swirl direction of the hot air are the same direction. The recovery means 10 of the processing apparatus is provided on the outer peripheral portion of the processing chamber so as to maintain the swirling direction of the swirled powder particles. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied from the outer peripheral portion of the apparatus to the processing chamber peripheral surface from the horizontal and tangential directions. The swirl direction of the pulverized product supplied from the powder particle supply port 14, the swirl direction of the cool air supplied from the cold air supply means 8, and the swirl direction of the hot air supplied from the hot air supply means are all the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirl flow in the processing apparatus is strengthened, a strong centrifugal force is applied to the toner particles, and the dispersibility of the toner particles is further improved. Uniform heat-treated toner particles can be obtained.
If necessary, after the pulverization step or after the heat treatment step, an inertia classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.), a centrifugal classification type turboplex (manufactured by Hosokawa Micron Co.), a TSP separator (Hosokawa Micron). ), Faculty (manufactured by Hosokawa Micron Corporation), Ultrasonic (manufactured by Koei Sangyo Co., Ltd.), Resona Sieve, Gyroshifter (Tokuju Kosakusha Co., Ltd.), Turbo Screener (manufactured by Turbo Kogyo Co., Ltd.), High Volter ( Classification may also be performed using a sieving machine such as Toyo Hitec.
If necessary, surface modification of the pulverized product or heat-treated toner particles using a hybridization system (manufactured by Nara Machinery Co., Ltd.) or a mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.) after the pulverization step or after the heat treatment step. Processing can also be performed.
If necessary, inorganic fine particles or the like may be added to the pulverized product before the heat treatment step. As a method of adding inorganic fine particles and the like to the pulverized product, a predetermined amount of the pulverized product and inorganic fine particles are blended into powder such as Henschel mixer, Mechano Hybrid (manufactured by Nippon Coke), Super Mixer, Nobilta (manufactured by Hosokawa Micron). Stirring and mixing may be performed using a high-speed stirrer that gives a shearing force as an external additive.
In the present invention, the average circularity of the toner is preferably 0.960 or more and 1.000 or less, more preferably 0.965 or more and 1.000 or less. When the average circularity of the toner is in the above range, the toner transfer efficiency is improved. As the means for adjusting the average circularity of the toner within the above range, the above heat treatment step can be suitably exemplified.

Hereinafter, methods for measuring various physical properties of toner and raw materials will be described.
<Measurement of Glass Transition Temperature (Tg) of Resin Composition>
The glass transition temperature of the resin composition is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of the resin composition is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure in min.
Once the temperature is raised to 180 ° C. and held for 10 minutes, the temperature is then lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the range of 30 to 180 ° C. The temperature at the point where the straight line that is equidistant from the straight line extending the base line before and after the specific heat change at this time and the curve of the step change portion of the glass transition in the DSC curve intersects. And the glass transition temperature (Tg: ° C.) of the resin composition.

<Measurement of melting point of hydrocarbon wax and crystalline polyester resin>
The melting point (Tm) of the hydrocarbon wax and the crystalline polyester resin is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of hydrocarbon wax or crystalline polyester resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement temperature range is 20 to 180 ° C. Then, the measurement is performed at a heating rate of 10 ° C./min. In the measurement, the temperature is once raised to 180 ° C., subsequently lowered to 20 ° C., and then the temperature is raised again. The peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 to 180 ° C. in the second temperature raising process is defined as the melting point (° C.) of the hydrocarbon wax or crystalline polyester.

<Measurement of weight average molecular weight (Mw) of crystalline polyester resin>
The weight average molecular weight (Mw) of the crystalline polyester resin is measured as follows using gel permeation chromatography (GPC).
After 0.03 g of crystalline polyester resin is dispersed and dissolved in 10 ml of o-dichlorobenzene, it is allowed to stand at 135 ° C. for 24 hours for dissolution. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions.
[Analysis conditions]
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: Differential refractive index detector Shodex RI-71 (Showa Denko)
Separation column: TSK gel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
In calculating the molecular weight of the crystalline polyester resin, standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20 manufactured by Tosoh Corporation) was used. F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Measurement of Mass Ratio of Polyester Resin Component to Vinyl Resin Component in Resin Composition B>
In the resin composition B, the mass ratio of the polyester resin component to the vinyl resin component is measured by hydrolyzing the polyester resin component of the resin composition B.
Specifically, 50 ml of dioxane and 10 ml of a 10% by weight potassium hydroxide aqueous solution are added to 300 mg of the resin composition B, and the speed is about 2 reciprocations per second at 70 ° C. using a commercially available horizontal shaker. Shake for 6 hours to hydrolyze the polyester resin component of resin composition B.
Then, after cooling to room temperature, diethyl ether was added to carry out a liquid separation operation, washed with water, the solvent was distilled off from the separated organic layer under reduced pressure, and further dried in a 90 ° C. atmosphere under reduced pressure for 24 hours. [A (mg)].
And the mass ratio with respect to the vinyl resin component of the polyester resin component in the resin composition B is calculated | required by following Formula.
Mass ratio of polyester resin component to vinyl resin component in resin composition B = {(300-A) / 3}: {A / 3}

<Measurement of molecular weight of tetrahydrofuran-soluble component of resin composition>
The molecular weight distribution of the tetrahydrofuran (THF) soluble part of the resin composition is measured by gel permeation chromatography (GPC) as follows.
The resin composition is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F— 4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement method of softening point of resin>
The softening point of the resin is measured according to a manual attached to the apparatus using a constant load extrusion type capillary rheometer “Flow Characteristics Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation).
In this apparatus, while applying a constant load from the upper part of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between the piston lowering amount and the temperature at this time is obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the sample outflow is finished and the piston lowering amount Smin at the time when the sample outflow starts is obtained (this is assumed to be X. X = (Smax). -Smin) / 2). Then, the temperature on the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.
The measurement sample was 1.0 g of resin, compression-molded for 60 seconds at 10 MPa using a tablet molding compressor (NT-100H, manufactured by NPA Corporation) in an environment of 25 ° C., and a cylindrical shape having a diameter of 8 mm. Use what you did.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measure with 25,000 effective measurement channels, analyze and calculate the measurement data.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter).
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using
The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows.
(1) Place 200 ml of electrolyte in a glass 250 ml round bottom beaker for exclusive use of Multisizer 3 and set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) 30 ml of electrolyte solution is put into a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measuring instrument washing is used as a dispersant. 0.3 ml of a diluted solution obtained by diluting a 10 mass% aqueous neutral detergent solution (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass is added.
(3) Built-in two oscillators with an oscillation frequency of 50 kHz with a phase shifted by 180 degrees, and in an aquarium of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W Is charged with a predetermined amount of ion-exchanged water, and 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolyte solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolyte solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of average circularity of toner>
The average circularity of the toner is measured using a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows.
First, 20 ml of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.2 ml of a diluted solution obtained by diluting 3) times with ion-exchanged water.
Further, 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervo Creer)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Exchange water is added, and 2 ml of Contaminone N is added to this water tank.
For the measurement, a flow type particle image analyzer equipped with a standard objective lens (10 ×) is used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid.
The dispersion prepared in accordance with the above procedure is introduced into a flow type particle image analyzer, and 3000 toners are measured in the HPF measurement mode and the total count mode.
Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner is obtained.
In the measurement, automatic focus adjustment is performed using standard latex particles ("DISE Scientific AND RESPARTIC AND TEST PARTILES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water) before starting the measurement. Thereafter, focus adjustment is performed every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.
<Production Example of Crystalline Polyester Resin A1>
Reaction of raw material monomer and tin octoate (II) shown in Table 1 (corresponding to 0.5 parts by mass with respect to 100 parts by mass of raw material monomer) with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple Put in the tank. Next, the temperature was gradually raised while stirring in a nitrogen gas atmosphere, and the reaction was performed at 160 ° C. with stirring for 5 hours. Thereafter, the pressure in the reaction vessel was lowered to 8.3 kPa, the temperature was raised to 200 ° C., and the reaction was performed for 4 hours (first reaction step).
Thereafter, the pressure in the reaction vessel was gradually released and returned to normal pressure, 7.0 mol% of octadecanoic acid was added to the total mol% of the raw material monomers, and the reaction was performed at 200 ° C for 2 hours under normal pressure. . Thereafter, the inside of the reaction vessel was again decompressed to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain crystalline polyester resin A1 (second reaction step).
The crystalline polyester resin A1 had a weight average molecular weight (Mw) of 1.01 × 10 ⁴ and a melting point of 75 ° C.

<Production example of crystalline polyester resins A2 to A9>
In the production example of the crystalline polyester resin A1, the type and amount of the alcohol component and / or carboxylic acid component in the first reaction step are changed as shown in Table 1, and the type and amount of the monomer in the second reaction step are changed. Except for the change, the reaction was performed in the same manner to obtain crystalline polyester resins A2 to A9. Table 1 shows the physical properties of the crystalline polyester resins A2 to A9.

<Example of production of resin composition B1>
A polyester resin monomer other than trimellitic acid shown in Table 2, an amphoteric compound, and 15 parts of tin (II) dioctanoate as an esterification catalyst are placed in a four-necked flask, and a thermometer, a stir bar, a condenser, and A nitrogen introduction tube was attached, and polymerization was performed at 230 ° C. for 4.5 hours in a nitrogen atmosphere.
Thereafter, once cooled to 160 ° C., 150 parts of trimellitic acid was added. Subsequently, the mixture of the monomer for styrene resins shown in Table 2 and 30 parts of dicumyl peroxide as a polymerization initiator was added dropwise at 160 ° C. over 2 hours. After completion of the dropping, the temperature was further raised to 200 ° C., and the reaction was carried out for 3 hours until the softening point reached 115 ° C.

<Production Examples of Resin Compositions B2 to B5>
Except having changed into the raw material and usage-amount shown in Table 2, it reacted similarly to the manufacture example of resin composition B1. In either case, the reaction time was appropriately changed until the softening point reached 115 ° C., and the reaction was advanced to obtain resin compositions B2 to B5.

<Production Example of Resin Composition B6>
Put the monomer for polyester resin shown in Table 2 and 15 parts of tin (II) dioctanoate into a four-necked flask, attach a thermometer, stir bar, condenser and nitrogen inlet tube, and react at 220 ° C. for 6 hours in a nitrogen atmosphere. To obtain a polyester resin.

<Example of production of resin composition C1>
20 parts by mass of polyethylene (weight average molecular weight: 1400, number average molecular weight: 850, endothermic peak temperature by DSC is 100 ° C.)
-Styrene 60 parts by mass-Acrylic acid-n-butyl 16 parts by mass-Acrylonitrile 4 parts by mass-Xylene 20 parts by mass The mixture of the above raw materials was charged into an autoclave, and the autoclave was purged with nitrogen. Held at 0C. Next, 50 parts by mass of a 2% by mass di-tert-butyl peroxide xylene solution was continuously added dropwise to the mixture over 5 hours. Then, it cooled, the solvent was isolate | separated and removed, and the resin composition C1 which the vinyl copolymer graft-bonded to polyethylene was obtained. The glass transition temperature (Tg) of the resin composition C1 is 61 ° C. The molecular weight by GPC of the THF soluble part of the resin composition C1 is 7400 for the weight average molecular weight (Mw) and 2800 for the number average molecular weight (Mn). there were. In the GPC measurement, no peak corresponding to the raw material polyethylene was observed.

<Production Examples of Resin Compositions C2 to C7>
In the manufacture example of resin composition C1, it reacted similarly except having changed so that it might become a raw material and usage-amount shown in Table 3, and obtained resin composition C2-C7. Table 3 shows the physical properties of the resin compositions C2 to C7.

<Table 3>

<Production Example of Toner 1>
Resin composition B3 100 parts by weight Crystalline polyester resin A1 10 parts by weight Resin composition C5 5 parts by weight Wax 2 (see Table 4) 5 parts by weight Copper phthalocyanine (CI Pigment Blue 15: 3) 6.5 parts by mass, 0.3 parts by mass of 3,5-di-t-butylsalicylic acid aluminum compound (Bontron E88 manufactured by Orient Chemical Industries)
The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min. And kneaded with a mold, manufactured by Ikegai Co., Ltd. The obtained kneaded product was cooled to 25 ° C., and then coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, using a Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.), the classification rotor was classified at 130 s ⁻¹ and the dispersion rotor was classified at 120 s ⁻¹ to obtain toner particles 1.
Next, heat treatment toner particles were obtained by using the obtained toner particles 1 and performing heat treatment with the treatment apparatus shown in FIG.
The operating conditions of the processing apparatus were as follows.
Feed amount = 5 kg / hr, hot air temperature = 170 ° C., hot air flow rate = 6 m ³ / min. Cold air temperature = −5 ° C., cold air flow rate = 4 m ³ / min. , Blower airflow = 20 m ³ / min. , Compressed gas flow rate = 1 m ³ / min. .
Furthermore, the heat treatment the toner particles of 100 parts by weight, 1.0 part by weight of hydrophobic silica (BET specific surface area: 200m ² / g), and titanium oxide fine particles (BET specific surface area surface-treated with isobutyl trimethoxysilane: ^{80 m} 2 / g) Toner 1 was obtained by mixing 1.0 part by mass with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min.
Toner 1 had a weight average particle diameter (D4) of 4.8 μm and an average circularity of 0.975. The physical properties of the toner are shown in Table 5.

<Production Example of Toners 2 to 33>
In the production example of the toner 1, except that the types and addition amounts of the crystalline polyester resin A, the hydrocarbon wax, the resin composition B, and the resin composition C were adjusted according to Table 5, the same as the production example of the toner 1, Toners 2 to 33 were obtained. For only the toner 24, the heat treatment step by the processing apparatus shown in FIG.

<Example of production of magnetic core particle 1>
Step 1 (weighing and mixing step):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 parts by mass Ferrite raw materials were weighed so that the above composition ratio was the above. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using stainless beads having a diameter of 1/8 inch.
-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (grinding step):
After pulverizing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).
-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 100 parts by mass of polyvinyl alcohol as a binder are added to 100 parts by mass of the calcined ferrite, and a spray dryer (manufacturer: Okawara Kako) is used. Granulated into spherical particles. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours to remove the organic components of the dispersant and the binder.
-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.
-Process 6 (screening process):
After crushing the agglomerated particles, the low-magnetic force product is cut by magnetic separation, and the coarse particles are removed by sieving with a sieve having an opening of 250 μm, and a 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Adjustment of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3 mass%
Azobisisobutyronitrile 2.0% by mass
Among the above materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone are put into a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirring device. Nitrogen gas was introduced to make the atmosphere sufficiently nitrogen, and then heated to 80 ° C. Thereafter, azobisisobutyronitrile was added and refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain coating resin 1.
30 parts by mass of the obtained coating resin 1 was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal 330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 ml / 100 g
)
Was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of production of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was added to 100 parts by mass of the magnetic core particles 1 in a vacuum deaeration type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component. After the addition, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and after the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure.
The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

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

<Production example of two-component developer 2-33>
In the production example of the two-component developer 1, the same operation was performed except that the combination of toners was changed as shown in Table 6 to obtain two-component developers 2-33.

<Example 1>
(Low temperature fixability)
A developer unit containing the two-component developer 1 was mounted on the cyan station of a Canon full color copier imagePRESS C1 +, and the image was formed so that an image could be formed with the fixing unit removed. Using the modified machine, a toner image (hereinafter, non-fixed image) not fixed on the evaluation paper was formed.
As the evaluation paper, color copier / printer plain paper GF-C104 (A4, 104 g / cm ² ) (sold by Canon Marketing Japan Inc.) was used.
Actually, the development conditions are adjusted as appropriate so that the amount of toner on the paper for the FFH image (hereinafter, solid portion) is 1.2 mg / cm ² , 3 cm from the leading edge of the evaluation paper (A4 length), and An unfixed image of 2 cm × 10 cm was formed at the center position of the evaluation paper. The unfixed image was conditioned for 24 hours in a low-temperature and low-humidity environment (15 ° C./10% Rh).
Subsequently, the fixing device was taken out from Canon full-color copying machine imageRUNNER ADVANCE C9075PRO, and a fixing test jig was prepared so that the process speed and upper and lower fixing member temperatures (belt temperatures) could be controlled independently.
The fixing test jig was set as follows.
Process speed: 450mm / sec
Lower belt temperature: fixed at 100 ° C. Upper belt temperature: adjusted every 5 ° C. within a range of 100 ° C. to 200 ° C. In a low temperature and low humidity environment (15 ° C./10% Rh), using the fixing test jig set as described above, The humidity-adjusted unfixed image was passed through to obtain a fixed image.
The obtained fixed image is rubbed 5 times with a lens cleaning wiper (Dasper Ozu Sangyo Co., Ltd.) applied with a load of 4.9 kPa, and the density reduction rate of the image density before and after the rubbing becomes 10% or less. The point was taken as the fixing temperature.
Under the criterion that fixing is not possible when the density drop exceeds 10%, the lowest upper belt set temperature that does not exceed 10% of the image density reduction rate is set as the low temperature fixing temperature, and evaluation is performed according to the following evaluation standards. .
(Evaluation criteria)
A: Less than 120 ° C (excellent)
B: 120 ° C. or higher and lower than 130 ° C. (a little better)
C: 130 ° C. or higher and lower than 140 ° C. (prior art level; acceptable level in the present invention)
D: 140 ° C. or higher (inferior to conventional level; impractical level in the present invention)

(Hot offset property)
Similarly to the evaluation of the low-temperature fixability, the two-component developer 1 was placed in a cyan station of a Canon full-color copying machine imagePRESS C1 + to prepare an unfixed image for evaluation.
As the evaluation paper, color copier / printer plain paper CS680 (A4, 68 g / m ² ) (sold by Canon Marketing Japan Inc.) was used.
Actually, the development conditions were adjusted so that the amount of toner applied on the paper of the FFH image (hereinafter, solid portion) was 0.08 mg / cm ² to obtain an unfixed FFH image.
After that, as in the low-temperature fixability evaluation, evaluation was performed in a normal temperature and low humidity environment (23 ° C / 5% Rh) using a fixing evaluation jig obtained by modifying a fixing device removed from the Canon full color copier imageRUNNER ADVANCE C9075PRO. It was.
The reflectivity of the evaluation paper before image printing is reflected by the reflectometer ("REFLECTOMETER"
Measured by “MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the average value measured at five locations was defined as D _A (%). The fixing temperature in the fixing evaluation jig is adjusted every 5 ° C. within the range of 100 to 200 ° C., the reflectance of the white background portion of the fixed image at each fixing temperature is measured with a reflectometer, and the maximum value is expressed as D _B (% ).
The difference between D _A (%) and D _B (%) did not exceed 0.5%, and the highest fixing temperature was set as the fixing upper limit temperature, and the hot offset property was evaluated according to the following criteria.
(Evaluation criteria)
A: 200 ° C. or higher (excellent)
B: 180 ° C. or higher and lower than 200 ° C. (a little better)
C: 160 ° C. or higher and lower than 180 ° C. (prior art level; acceptable level in the present invention)
D: Less than 160 ° C. (Inferior to conventional level; impractical level in the present invention)

(Fixable width)
The difference between the low-temperature fixing temperature and the upper limit fixing temperature was defined as the fixable width, and the width of the fixable temperature range was evaluated.
(Evaluation criteria)
A: 80 ° C. or higher (excellent)
B: 65 ° C. or higher and lower than 80 ° C. (A little better)
C: 35 ° C. or more and less than 65 ° C. (prior art level; acceptable level in the present invention)
D: less than 35 ° C. (Inferior; not practical in the present invention)

(Transfer characteristics [white spot level])
As an image forming apparatus, a Canon full-color copier imageRUNNER ADVANCE C9075 PRO was used, and the two-component developer 1 was put in the developing unit at the cyan position, and an image output test was conducted to evaluate the transfer characteristics.
In the image output test, the toner loading amount on the paper was adjusted to 0.35 mg / cm ² (FFh image), and the evaluation paper (A4 paper; CS-) was used in a high temperature and high humidity environment (30 ° C./85% RH). 680, 68.0 g / m ² , sold by Canon Marketing Japan Inc.), 50,000 continuous FFh band charts were output continuously.
Thereafter, a solid image having an image ratio of 100% was output on the evaluation paper, and the number of white spots in the image was visually confirmed.
(Evaluation criteria)
1: Less than 5 white spots (excellent)
2: White spots are 5 or more and less than 10 (good)
3: White spots are 10 or more and less than 20 4: White spots are 20 or more and less than 30 5: White spots are 30 or more and less than 40 6: White spots are 40 or more and less than 50 7: White spots are 50 More than 60 and less than 60 (this is a level that is not a problem in the present invention)
8: 60 to less than 70 white spots (8 or less is an unacceptable level in the present invention)
9: 70 to less than 80 white spots 10: 80 or more white spots

(Transfer efficiency)
As an image forming apparatus, a full-color copying machine imageRUNNER ADVANCE C9075 PRO made by Canon was used, and 50,000 sheets were continuously output under the same conditions as the evaluation of the transfer characteristics [white spot level].
Thereafter, the copying machine was stopped during the development of a solid image having an image ratio of 100% on the evaluation paper, and the transfer residual toner on the latent image carrier at the time of image formation was stripped off using a transparent polyester adhesive tape. A density difference was calculated by subtracting the density of the adhesive tape only applied on the paper from the density of the adhesive tape peeled off on the paper, and the evaluation was performed based on the following evaluation criteria.
For density measurement, an X-Rite color reflection densitometer (X-Rite) was used. (Evaluation criteria)
A: Density difference is less than 0.10 (very good)
B: Concentration difference is 0.10 or more and less than 0.15 (good)
C: Concentration difference is 0.15 or more and less than 0.25 (this is a level that is not a problem in the present invention)
D: The density difference is 0.25 or more (not acceptable in the present invention)

<Examples 2 to 23 and Comparative Examples 1 to 10>
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 2-33 shown in Table 6 were used. The evaluation results are shown in Table 6.

  1. 1. Raw material quantitative supply means, 2. compressed gas flow rate adjusting means; 3. Introducing tube, 4. Protruding member, 5. supply pipe, 6. processing chamber; Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. 11. Hot air supply means outlet, 12. distribution member; Swivel member, 14. Powder particle supply port

Claims (7)

By cooling the mixture containing crystalline polyester resin A, resin composition B, resin composition C, and hydrocarbon wax after melt-kneading, pulverizing the obtained kneaded material, and heat-treating the obtained pulverized material A toner having toner particles obtained,
(1) The resin composition B is a hybrid resin obtained by chemically bonding a polyester resin component and a vinyl resin component,
(2) The resin composition C is a polymer obtained by reacting a hydrocarbon compound and a vinyl resin component,
(3) The melting point of the crystalline polyester resin A measured by a differential scanning calorimeter (DSC) is T1 (° C.), the melting point of the hydrocarbon wax is T2 (° C.), and the glass transition temperature of the resin composition C. And a toner satisfying the following relationship when T3 (° C.).
| T3-T1 | ≦ 15 (Formula 1)
| T2-T1 | ≦ 15 (Formula 2)
60 ° C. ≦ T1 ≦ 85 ° C. (Formula 3)   The crystalline polyester resin A includes an alcohol component containing at least one compound selected from the group consisting of an aliphatic diol having 6 to 12 carbon atoms and derivatives thereof, and an aliphatic having 6 to 12 carbon atoms. The toner according to claim 1, which is a resin obtained by condensation polymerization of a carboxylic acid component containing at least one compound selected from the group consisting of dicarboxylic acids and derivatives thereof.   The toner according to claim 1, wherein a content of the crystalline polyester resin A is 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin composition B.   The toner according to claim 1, wherein the content of the crystalline polyester resin A is equal to or more than the content of the resin composition C.   The toner according to claim 1, wherein a mass ratio of the polyester resin component to the vinyl resin component in the resin composition B is 50:50 to 95: 5.   The crystalline polyester resin A is a kind selected from the group consisting of an aliphatic monocarboxylic acid having 10 to 20 carbon atoms and an aliphatic monoalcohol having 10 to 20 carbon atoms at the end of the crystalline polyester resin A. The toner according to claim 1, wherein the aliphatic compound is a resin bonded by condensation.   The toner according to claim 1, wherein the toner particles are toner particles obtained by heat treatment with hot air.

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