JP2018045092A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low temperature fixability and chargeability without being affected by storage environment.SOLUTION: A toner has toner particles containing a resin component, where the resin component has an olefinic ester group-containing copolymer which has a unit Y1 represented by formula (1), and at least one unit Y2 selected from a unit Y2-1 represented by formula (2) and a unit Y2-2 represented by formula (3), has a concentration of an ester group of 2-18 mass% with respect to the total mass of an olefinic ester group-containing copolymer; and an α-olefin copolymer which has a unit Y3 represented by formula (4) and a unit Y4 represented by formula (5), has a content of the unit Y4 of 5-50 mass with respect to the total mass of the α-olefin copolymer, and has such crystallinity that a melting point of 50-100°C, where a content of the olefinic ester group-containing copolymer contained in the resin component is 50 mass% or more with respect to the total mass of the resin component.SELECTED DRAWING: None

Description

  The present invention relates to a dry toner used in an electrophotographic system.

In recent years, with increasing demands for energy saving in image formation, efforts have been made to lower the toner fixing temperature. As one of the methods for improving the low-temperature fixability, there has been proposed a technique using a crystalline polyester resin having sharp melt properties in which the viscosity is greatly reduced when the melting point is exceeded (Patent Documents 1 to 3).
As another method, it has been proposed to lower the fixing temperature by using a resin having a low glass transition temperature. As a resin having a low glass transition temperature, a toner containing an ethylene ester group-containing copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-methyl acrylate copolymer has been proposed (Patent Documents 4 to 10). ).

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No.62-39428 Japanese Patent Laid-Open No. 4-120554 JP 2011-107261 A JP-A-11-202555 JP-A-8-184986 JP-A-4-21860 Japanese Patent Laid-Open No. 3-150576 JP 59-18854 A JP 58-95750 A

  When a conventional crystalline polyester resin was used as a resin for an electrophotographic toner, it exhibited excellent low-temperature fixability due to the sharp melt property of the resin. However, the crystalline polyester resin has a low electrical resistance and has a problem in toner charge retention.

  Therefore, the present inventors paid attention to a copolymer having an olefin-based unit such as ethylene or propylene as a resin having a high volume resistance and a glass transition temperature of room temperature or lower. Specifically, an ethylene (propylene) -acetate copolymer such as an ethylene-vinyl acetate copolymer or an ethylene (propylene) -acrylate ester such as an ethylene-methyl acrylate copolymer. An attempt was made to achieve both low-temperature fixability and charge retention using an ethylene (propylene) -methacrylate copolymer such as a copolymer and an ethylene-methyl methacrylate copolymer. However, it is difficult to satisfy low-temperature fixability under high-speed conditions only by partially including these olefinic ester group-containing copolymers in the toners proposed in Patent Documents 4 to 8. It was.

  On the other hand, when these olefinic ester group-containing copolymers are used as a toner main resin as described in Patent Documents 9 and 10, excellent low-temperature fixability can be obtained, but the olefinic ester group-containing copolymer is There is a problem in storage stability because it has crystallinity, grows in a high-temperature and high-humidity environment such as a storage environment, and the low-temperature fixability deteriorates.

  As a result of intensive studies by the present inventors, ethylene (propylene) -acetate copolymer such as ethylene-vinyl acetate copolymer, ethylene (propylene) -acrylic acid such as ethylene-methyl acrylate, etc. Ester copolymers, ethylene (propylene) -methacrylate copolymers such as ethylene-methyl methacrylate, etc., and mixtures thereof are used as main resins, and α-olefin copolymers are used in combination. As a result, it became clear that a toner having a stable low-temperature fixability can be obtained without being affected by the storage environment. Olefin ester group-containing copolymers such as ethylene (propylene) -acetate copolymer, ethylene (propylene) -acrylic ester copolymer, ethylene (propylene) -methacrylic ester copolymer, The α-olefin copolymer is considered to exist without causing complete phase separation in the toner because it has higher compatibility than the chemical structure similarity. Furthermore, since the α-olefin copolymer has a side chain and the side chain is short, the crystallization of the olefin ester group-containing copolymer is inhibited, and the α-olefin copolymer is crystallized. Therefore, it is considered that crystal growth hardly occurs even after storage in a high-temperature and high-humidity environment, and the low-temperature fixability is excellent.

（式中、Ｒ^１はＨまたはＣＨ_３であり、Ｒ^２はＨまたはＣＨ_３であり、Ｒ^３はＣＨ_３またはＣ_２Ｈ_５であり、Ｒ^４はＨまたはＣＨ_３であり、Ｒ^５はＣＨ_３またはＣ_２Ｈ_５であり、Ｒ^６はＣｎＨ２ｎ＋１（ｎは２以上６以下の整数）である。） That is, the toner of the present invention is
A toner having toner particles containing a resin component,
The resin component has, as a binder resin, an olefin ester group-containing copolymer and an α-olefin copolymer,
The olefin ester group-containing copolymer is a unit Y1 represented by the following formula (1):
Having at least one unit Y2 selected from the group of unit Y2-1 represented by the following formula (2) and unit Y2-2 represented by the following formula (3),
The ester group concentration is 2% by mass or more and 18% by mass or less with respect to the total mass of the olefinic ester group-containing copolymer,
The α-olefin copolymer is
A unit Y3 represented by the following formula (4);
It has unit Y4 shown by the following formula (5),
The content of the unit Y4 is 5% by mass or more and 50% by mass or less with respect to the total mass of the α-olefin copolymer,
Having a crystallinity of a melting point of 50 ° C. or higher and 100 ° C. or lower,
A toner in which the content of the olefinic ester group-containing copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component.

Wherein R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is CH ₃ or C ₂ H ₅ , R ⁴ is H or CH ₃ , R ⁵ is CH ₃ or C ₂ H ₅ and R ⁶ is CnH2n + 1 (n is an integer of 2 or more and 6 or less).

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and excellent in chargeability without being affected by the storage environment.

  In the present invention, the resin component means a polymer component mainly contributing to fixing performance. The resin component includes an olefin ester group-containing copolymer and an α-olefin copolymer.

（式中、Ｒ^１はＨまたはＣＨ_３であり、Ｒ^２はＨまたはＣＨ_３であり、Ｒ^３はＣＨ_３またはＣ_２Ｈ_５であり、Ｒ^４はＨまたはＣＨ_３であり、Ｒ^５はＣＨ_３またはＣ_２Ｈ_５である。） <Olefin ester group-containing copolymer>
In the present invention, the olefin ester group-containing copolymer is a polymer in which an ester group unit is introduced into a polyolefin skeleton by means of copolymerization or the like, and specifically, a unit Y1 represented by the following formula (1): And at least one unit Y2 selected from the group of unit Y2-1 represented by the following formula (2) and unit Y2-2 represented by the following formula (3).

Wherein R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is CH ₃ or C ₂ H ₅ , R ⁴ is H or CH ₃ , R ⁵ is CH ₃ or C ₂ H ₅ )

  Hereinafter, at least one unit Y2 selected from the group of the unit Y2-1 represented by the formula (2) and the unit Y2-2 represented by the following formula (3) will be specifically described.

In the unit Y1 represented by the formula (1) and the unit Y2-1 represented by the formula (2), the olefin ester group-containing copolymer is represented by R ¹ being H, R ² being H, R ^A copolymer in which ³ is CH ₃ .
Since an ethylene-vinyl acetate copolymer can be designed with a low melting point, it is preferable from the viewpoint of low-temperature fixability. Further, in the unit Y1 represented by the formula (1) and the unit Y2-2 represented by the formula (3), the olefin-based ester group-containing copolymer has R ¹ as H, R ⁴ as H, and R ^5. In the ethylene-methyl acrylate copolymer in which is CH ₃ , the unit Y1 represented by the formula (1) and the unit Y2-2 represented by the formula (3), R ¹ is H, R ⁴ is H, R ⁵ Is a C ₂ H ₅ copolymer, an ethylene-ethyl acrylate copolymer, and a unit Y1 represented by the formula (1) and a unit Y2-2 represented by the formula (3), wherein R ¹ is H An ethylene-methyl methacrylate copolymer in which R ⁴ is CH ₃ and R ⁵ is CH ₃ is preferred from the viewpoint of storage stability under high temperature and high humidity because of high chemical stability.
One or more of the olefinic ester group-containing copolymers may be contained in the resin component.

  The total mass of the olefinic ester group-containing copolymer is Z1, the masses of the units Y1, Y2-1, and Y2-2 represented by the formula (1), formula (2), and formula (3) are l and m, respectively. , N. The value of (l + m + n) / Z1 of the olefin ester group-containing copolymer contained in the resin component is preferably 0.80 or more from the viewpoint of low-temperature fixability and charge maintenance, and is 0.95 or more. More preferably, it is more preferably 1.00.

Examples of units other than the units Y1 and Y2 that may be included in the olefin ester group-containing copolymer include, for example, the units represented by the following formula (6) and the following formula (7). Units. These may be introduced by adding a corresponding monomer in the copolymerization reaction for producing the olefinic ester group-containing copolymer, or by modifying the olefinic ester group-containing copolymer by a polymer reaction. it can.

  However, the acidic functional group deteriorates the charge maintenance property. Therefore, the acid value of the olefinic ester group-containing copolymer is 10 mgKOH / g or less, preferably 5 mgKOH / g or less, and more preferably substantially 0 mgKOH / g.

  The olefinic ester group-containing copolymer needs to be contained in an amount of 50% by mass or more, more preferably 70% by mass or more based on the total mass of the resin component, from the viewpoint of low-temperature fixing. Since the olefin-based ester group-containing copolymer has a glass transition temperature of 0 ° C. or less, the low-temperature fixability is improved when it is contained in the resin component by 50% by mass or more.

The olefinic ester group-containing copolymer needs to have an ester group concentration of 2% by mass to 18% by mass with respect to the total mass. Further, the ester group concentration is preferably 3% by mass or more and 10% by mass or less with respect to the total mass from the viewpoints of charge maintenance and low temperature fixability. When the ester group concentration of the olefinic ester group-containing copolymer is 18% by mass or less, the charge retention as a toner is improved. On the other hand, when the ester group concentration of the olefinic ester group-containing copolymer is 2% by mass or more, the adhesion to paper is improved and the low-temperature fixability is improved. The ester group concentration of the present invention is a value indicating how much the ester group [—C (═O) O—] bonding site in the resin is contained in mass%, and is specifically represented by the following formula. Value.
Ester group concentration (unit:%) = [(N × 44) / number average molecular weight] × 100
Here, N is the average number of ester groups per molecule of the olefinic ester group-containing copolymer, and 44 is the formula weight of the ester group [—C (═O) O—].
In calculating the actual ester group concentration, there is a method of calculating and calculating the monomer composition and the number of ester groups constituting the olefinic ester group-containing copolymer by nuclear magnetic resonance spectrum (NMR) or the like.

  In order to control the ester group concentration of the olefinic ester group-containing copolymer, the average of the unit Y2 of the olefinic ester group-containing copolymer is based on the total mass of the olefinic ester group-containing copolymer. It is necessary that the content is 3% by mass or more and 35% by mass or less, and 5% by mass or more and 20% by mass or less is preferable from the viewpoint of charge maintenance. When the ratio of the unit Y2 of the olefin ester group-containing copolymer is 35% by mass or less, the charge retention as a toner is improved. On the other hand, when the average ratio of the unit Y2 of the olefinic ester group-containing copolymer is 3% by mass or more, the adhesion to paper is improved and the low-temperature fixability is improved.

  The masses l, m, n of the units Y1, Y2-1, Y2-2 and the ratio of the unit Y2 can be measured using a general analytical method, for example, nuclear magnetic resonance (NMR) or thermal Techniques such as decomposition gas chromatography can be applied.

Measurement by ¹ H NMR is performed by the following method. Bonded to the hydrogen of the alkenyl represented by the above formula (1) of the unit Y1, the hydrogen of the acetyl group represented by the above formula (2) of the unit Y2-1, and the oxygen represented by the above formula (3) of the unit Y2-2. Each unit ratio can be calculated by comparing the integration ratio of methyl group or ethylene group hydrogen.

Specifically, calculation of the unit ratio of the ethylene-vinyl acetate copolymer (unit ratio derived from vinyl acetate: 15% by mass) includes about 5 mg of a sample as an internal standard in which tetramethylsilane has a chemical shift of 0.00 ppm. A solution of 0.5 ml of heavy acetone dissolved in a sample tube is placed in a sample tube, ¹ H NMR is measured under the conditions of a repetition time of 2.7 seconds and an accumulation count of 16 times. A peak of 1.14 to 1.36 ppm is observed. Since the peak in the vicinity of 2.04 ppm corresponds to CH ₃ of the vinyl acetate unit, which corresponds to CH ₂ —CH ₂ of the ethylene unit, the ratio of the integrated values of those peaks was calculated.

The olefin ester group-containing copolymer preferably has a melt flow rate of 5 g / 10 min to 30 g / 10 min. When the melt flow rate is less than 5 g / 10 min, the glossiness of the image is inferior, and when the melt flow rate is greater than 30 g / 10 min, the strength as a toner is low and the toner is blocked during storage. Further, from the viewpoint of enduring impact and pressure when using the toner, 20 g / 10 min or less is more preferable.
The melt flow rate was measured based on JIS K 7210 under conditions of 190 ° C. and a load of 2160 g. When the resin component contains a plurality of the olefin ester group-containing copolymers, the melt flow rate was measured under the above conditions after melt mixing.

  The melt flow rate can be controlled by changing the molecular weight of the olefinic ester group-containing copolymer, and the melt flow rate can be lowered by increasing the molecular weight. Specifically, the molecular weight of the olefin-based ester group-containing copolymer is preferably 50,000 or more, more preferably 100,000 or more. The molecular weight of the olefinic ester group-containing copolymer is preferably 500,000 or less from the viewpoint of image gloss.

The olefin ester group-containing copolymer preferably has a breaking elongation of 300% or more, and more preferably 500% or more. When the breaking elongation is 300% or more, the bending resistance of the fixed product is improved.
The breaking elongation was measured under conditions based on JIS K 7162. When the binder resin contains a plurality of the olefinic ester group-containing copolymers, the elongation at break was measured according to the above conditions after being melt-mixed.

<Α-olefin copolymer>
The toner of the present invention contains an α-olefin copolymer having a crystallinity with a melting point of 50 ° C. or higher and 100 ° C. or lower as a resin component.

（式中、Ｒ^６はＣｎＨ２ｎ＋１（ｎは２以上６以下の整数）である。） The α-olefin copolymer is a polymer in which a side chain having a hydrocarbon group is introduced into a polyolefin skeleton by a means such as copolymerization, specifically, a unit Y3 represented by the following formula (4); It has unit Y4 shown by the following formula (5).

(In the formula, R ⁶ is CnH2n + 1 (n is an integer of 2 or more and 6 or less).)

Hereinafter, the unit Y4 represented by the formula (5) will be specifically described.
The α-olefin copolymer is a copolymer in which R ⁶ is C _n H _{2n + 1} (n is an integer of 2 or more and 6 or less) in the unit Y4 represented by the formula (5). When the number of carbon atoms in the side chain is 1 or less, the crystallinity is too high, so that the crystal grows in a storage environment and the low-temperature fixability deteriorates. Therefore, it becomes difficult to achieve both blocking resistance and low-temperature fixability.
Among the α-olefin copolymers, the ethylene-butene copolymer, which is a random copolymer of ethylene and 1-butene, has crystallinity and can be designed to have a low melting point, which is preferable from the viewpoint of low-temperature fixability. .
One or a plurality of the α-olefin copolymers may be contained in the resin component.

  The total mass of the α-olefin copolymer is Z2, the unit Y3, and the unit Y4 are o and p, respectively. The (o + p) / Z2 value of the α-olefin copolymer contained in the resin component is preferably 0.80 or more from the viewpoint of low-temperature fixability and charge maintenance, and is 0.95 or more. Is more preferable and 1.00 is still more preferable.

  Further, as long as the physical properties are not affected, an α-olefin copolymer composed of units other than unit Y3 and unit Y4 may be included, and the content thereof is an α-olefin copolymer composed of units Y3 and Y4. It is 20 mass% or less with respect to the total mass of a coalescence, Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, and it is still more preferable that it is substantially 0 mass%. The acid value of the α-olefin copolymer is 10 mgKOH / g or less, preferably 5 mgKOH / g or less, and more preferably substantially 0 mgKOH / g.

  The α-olefin copolymer is preferably contained in an amount of 5% by mass or more and 40% by mass or less, more preferably 10% by mass or more and 30% by mass or less, based on the total mass of the resin component. It is preferable because it inhibits and stable low-temperature fixability can be obtained. The proportion of the unit Y4 of the α-olefin copolymer needs to be 5% by mass or more and 50% by mass or less, and 10% by mass or more and 30% by mass with respect to the total mass of the α-olefin copolymer. The following is preferable from the viewpoint of anti-blocking resistance. Since the proportion of the unit Y4 of the α-olefin copolymer is 30% by mass or less, the degree of crystallinity is increased, so that anti-blocking resistance as a toner is improved. On the other hand, since the melting point of the α-olefin resin is lowered when the proportion of the unit Y4 of the α-olefin copolymer is 10% by mass or more, the low-temperature fixability is improved.

  The masses o and p of the unit Y3 and the unit Y4 and the ratio of the unit Y4 can be measured by using a general analysis method, such as nuclear magnetic resonance (NMR) or pyrolysis gas chromatography. Techniques can be applied.

Measurement by ¹ H NMR is performed by the following method. The unit ratio is calculated by comparing the integral ratio of the hydrogen of the alkenyl group represented by formula (4) of unit Y3 and the hydrogen of the alkenyl group represented by formula (5) of unit Y4 with the hydrogen of the methyl group. it can.

Specifically, the unit ratio of the ethylene-1-butene copolymer (unit ratio derived from butene: 16% by mass) was calculated by measuring about 5 mg of the sample, and tetramethylsilane was contained within 0.00 ppm of ¹ H NMR. A solution dissolved in 0.5 ml of deuterated benzene contained as a standard was put into a sample tube, and ¹ H NMR was measured under the conditions of a repetition time of 2.7 seconds and an integration number of 16 times, 1.14 to 1.36 ppm. Corresponds to CH ₂ —CH ₂ of the alkenyl group and the peak around 0.88 to 0.94 ppm corresponds to CH _{3 of the} 1-butene unit. Therefore, the ratio of the integrated values of these peaks was calculated. I did it.

  The crystalline polyester resin for toner of the present invention needs to have a crystallinity calculated by the following formula of 15% or more as measured by a wide angle X-ray diffraction method, more preferably 20% or more. preferable. When the degree of crystallinity is less than 15%, the viscosity of the toner tends to decrease, and the anti-blocking resistance is poor. On the other hand, the upper limit of the crystallinity needs to be 40% or less. When the crystallinity is larger than 40, it takes time to melt the toner when it is fixed, and the fixability is poor.

In the measurement by the wide-angle X-ray diffraction method, in the X-ray diffraction method, the sample is irradiated with X-rays, and from the obtained diffraction information (a wide-angle X-ray diffraction pattern or a wide-angle X-ray diffraction profile), a scattering region and a crystal derived from amorphous From the scattering region derived from the above, the ratio of the crystal scattering intensity to the total scattering intensity was calculated by the following formula.
Crystallinity (%) = ((crystal-derived scattering intensity) / (crystal-derived scattering intensity + amorphous-derived scattering intensity)) × 100

  The melting point of the α-olefin copolymer of the present invention is 50 ° C. or more and 100 ° C. or less, so that both low-temperature fixability and antiblocking properties can be achieved, and more preferably 60 ° C. or more and 80 ° C. or less. It is possible to achieve both low-temperature fixability and anti-blocking properties.

The melting point can be measured using a differential scanning calorimeter (manufactured by METTLER TOLEDO: DSC822 / EK90).
Specifically, a sample of 0.01 g or more and 0.02 g or less is precisely weighed in an aluminum pan and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the peak temperature of the melting endothermic peak is defined as the melting point.

Further, the toner of the present invention satisfies the following mathematical formula (1), and can achieve both stable blocking property and stable low-temperature fixability without being affected by the storage environment.
0.4 ≦ Wt / (W1 + W2 + Wn) ≦ 0.8 Formula (1)
Wt: endothermic amount derived from the crystalline resin of the toner of the present invention W1: endothermic amount of the olefinic ester group-containing copolymer of the present invention W2: endothermic amount of the α-olefin copolymer of the present invention Wn: toner of the present invention Endothermic amount of other crystalline materials

The endothermic amount can be measured using a differential scanning calorimeter (manufactured by METTLER TOLEDO: DSC822 / EK90).
Specifically, a sample of 0.01 g or more and 0.02 g or less is precisely weighed in an aluminum pan and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve.
It is obtained from the integral value of the difference between the baseline obtained by connecting the low temperature side baseline and the high temperature side baseline with a straight line across the endothermic peak of the obtained DSC curve and the endothermic peak at each temperature.

  When the value of the formula (1) is 0.4 or more and 0.8 or less, the α-olefin copolymer causes moderate inhibition of the olefin ester group-containing copolymer, and the antiblocking property is maintained. In addition, stable low-temperature fixability can be obtained without being affected by the storage environment. More preferably, when it is 0.5 or more and 0.7 or less, more excellent anti-blocking property and stable low-temperature fixability can be obtained without being affected by the storage environment.

<Olefinic acid group-containing copolymer>
The toner of the present invention preferably contains an olefinic acid group-containing copolymer having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less as a resin component. By containing an olefinic acid group-containing copolymer having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less, the carboxyl group of the olefinic acid group-containing copolymer forms a hydrogen bond with a hydroxyl group on the paper surface. The adhesion between the paper and the paper is increased, and the fixed material is not erased by the eraser.

  In the present invention, the olefinic acid group-containing copolymer is mainly composed of a polyolefin such as polyethylene or polypropylene, and further has an acid group, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, A polymer in which units such as vinyl sulfonate are introduced by means of copolymerization or the like. Moreover, as long as the physical properties are not affected, units other than the polyolefin and the acid groups may be included, and the content of the units other than the polyolefin and the acid groups is based on the total mass of the olefinic acid group-containing copolymer. 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably substantially 0% by mass. Moreover, it is preferable that it is a polymer which has an acid group which has polyethylene as a main component from a fixed viewpoint, and it is preferable that an acidic radical is a unit of acrylic acid and methacrylic acid from an adhesive viewpoint with paper. That is, an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer is preferable from the viewpoint of improving the adhesion between the toner and paper.

  The olefinic acid group-containing copolymer is preferably contained in an amount of 10% by mass to 50% by mass with respect to the total mass of the resin component, and more preferably 10% by mass to 30% by mass. When the content of the olefinic acid group-containing copolymer is less than 10% by mass, the adhesion to paper is deteriorated. When the content of the olefinic acid group-containing copolymer is more than 50% by mass, the environmental fluctuation of the charging property becomes large.

  The acid value of the olefinic acid group-containing copolymer used in the present invention needs to be 50 mgKOH / g or more and 300 mgKOH / g or less, more preferably 80 mgKOH / g or more and 200 mgKOH / g or less. When the acid value is 50 mgKOH / g or more, sufficient adhesion to paper is exhibited, and when it is 300 mgKOH / g or less, the chargeability is improved.

  The acid value is the number of mg of potassium hydroxide required to neutralize acid components such as free fatty acids and resin acids contained in 1 g of a sample. The measurement method is as follows according to JIS-K0070.

(1) Reagent / solvent: Toluene-ethyl alcohol mixture (2: 1) is neutralized with 0.1 mol / L potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.
Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 mL of ethyl alcohol (95% by volume).
-0.1 mol / L potassium hydroxide ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95% by volume) to 1 L, leave it for 2 to 3 days, and filter. The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).

(2) Operation Weigh accurately 1 to 20 g of resin as a sample, add 100 mL of the solvent and a few drops of the phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with the 0.1 mol / L potassium hydroxide ethyl alcohol solution, and the end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.
A = B × f × 5.661 / S
A: Acid value (mgKOH / g)
B: Amount of use of 0.1 mol / L potassium hydroxide ethyl alcohol solution (mL)
f: Factor of 0.1 mol / L potassium hydroxide ethyl alcohol solution S: Sample (g)

  In this invention, it is preferable that the melt flow rate of an olefinic acid group containing copolymer is 200 g / 10min or less, and when larger than that, it may block at the time of storage. The olefinic acid group-containing copolymer preferably has a melt flow rate of 10 g / 10 min or more from the viewpoint of adhesion between the toner and paper. When the melt flow rate is less than 10 g / 10 minutes, it becomes difficult to be compatible with the olefin ester group-containing copolymer present in the toner, and as a result, the adhesion to the paper is lowered when viewed as a whole toner. The melt flow rate of the olefinic acid group-containing copolymer can be measured by the same method as the melt flow rate of the olefinic ester group-containing copolymer described above.

  In the present invention, the melting point of the olefinic acid group-containing copolymer is preferably 50 ° C. or higher and 100 ° C. or lower from the viewpoint of low-temperature fixability and storage stability. When the melting point is 100 ° C. or lower, the low-temperature fixability is further improved. Further, when the melting point is 90 ° C. or lower, the low-temperature fixability is further improved. On the other hand, when the melting point is lower than 50 ° C., the storage stability tends to decrease.

The melting point of the olefinic acid group-containing copolymer can be measured using a differential scanning calorimeter (DSC).
Specifically, a 0.01 to 0.02 g sample is precisely weighed in an aluminum pan, and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the peak temperature of the endothermic peak is defined as the melting point.

  In the toner of the present invention, in addition to the olefinic ester group-containing copolymer and the olefinic acid group-containing copolymer, other polymers may be used in combination as the binder resin. Specifically, the following polymers can be used. Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Styrene copolymers such as acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic resins, acrylic resins, methacrylic resins, poly Examples thereof include vinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, and polypropylene resin.

<Plasticizer>
The toner of the present invention preferably contains an aliphatic hydrocarbon compound having a melting point of 50 ° C. or higher and 100 ° C. or lower with respect to 100 parts by mass of the binder resin.
When the aliphatic hydrocarbon compound is heated, the olefinic ester group-containing copolymer can be plasticized. Therefore, by containing an aliphatic hydrocarbon compound in the toner, the olefin ester group-containing copolymer forming a matrix at the time of heat-fixing the toner is plasticized, and the low-temperature fixability can be improved. Furthermore, the aliphatic hydrocarbon compound having a melting point of 50 ° C. or higher and 100 ° C. or lower also acts as a nucleating agent for the olefinic ester group-containing copolymer. Therefore, the micro motility of the olefin ester group-containing copolymer is suppressed, and the chargeability is improved. The aliphatic hydrocarbon compound is more preferably contained in an amount of 10 parts by mass to 30 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoints of low-temperature fixability and chargeability.
Specific examples of the aliphatic hydrocarbon compound include saturated hydrocarbon compounds having 20 to 60 carbon atoms, such as hexacosane, triacosane, and hexatriacosane.

<Release agent>
The toner of the present invention preferably contains silicone oil as a release agent. Release agents generally used for toners such as alkyl waxes tend to be compatible with the olefinic ester group-containing copolymer, and a release effect is hardly obtained. Further, the addition of silicone oil improves the dispersibility of the pigment in the toner and makes it easy to obtain a high density image.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, carboxyl-modified silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil. The viscosity of the silicone oil is preferably 5 mm ² / S or more and 1000 mm ² / S or less, and more preferably 20 mm ² / S or more and 1000 mm ² / S or less.
The amount of silicone oil added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of obtaining good separability while suppressing a decrease in fluidity. More preferably, they are 5 to 20 mass parts.

<Colorant>
The toner of the present invention may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. 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.

These colorants can be used alone or in combination, and further in a solid solution state. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in the toner.
In this invention, it is preferable that content of a coloring agent is 1 to 20 mass parts with respect to 100 mass parts of binder resin.

  The toner of the present invention preferably has a volume-based median diameter of 3.0 μm or more and 10.0 μm or less, preferably 4.0 or more and 7.0 μm or less, from the viewpoint of obtaining a high-definition image. More preferred.

<Toner production method>
The toner production method of the present invention can be carried out by a known toner production method such as suspension polymerization method, kneading and pulverization method, emulsion aggregation method, and dissolution suspension method, and is limited to any one of these methods. Is not to be done.

  Hereinafter, the toner production methods in the dissolution suspension method and the emulsion aggregation method are specifically exemplified, but are not limited thereto.

<Dissolution suspension method>
With the dissolution suspension method, a resin, a colorant, a release agent and the like are dissolved or dispersed in an organic solvent, and the resulting solution or dispersion is dispersed in a poor solvent such as water to the size of toner particles. In this state, the organic solvent is distilled off to produce a toner. In the dissolution suspension method, a toner is manufactured through a resin dissolution step, a granulation step, a solvent removal step, and a washing and drying step.

(Resin dissolution process)
In the resin dissolving step, for example, the olefinic ester group-containing copolymer and α-olefin copolymer of the present invention are heated and dissolved in an organic solvent to prepare a resin solution, and if necessary, the resin solution is added to the resin solution. It is a process for producing a resin composition by dissolving or dispersing other resins, plasticizers, colorants, release agents and the like.

Any solvent can be used as long as the organic solvent used is an organic solvent that dissolves the resin. Specific examples include toluene and xylene.
Although there is no restriction | limiting in the usage-amount of the said organic solvent, What is necessary is just the quantity used as the viscosity which can disperse | distribute and granulate a resin composition in an aqueous medium. Specifically, the mass ratio of the resin composition containing the polybutadiene having crystallinity of the present invention, the olefinic acid group-containing copolymer, other resins, plasticizers, colorants, release agents and the like to the organic solvent is 10 / 90 to 50/50 is preferable from the viewpoint of granulation properties and toner production efficiency described later.
On the other hand, the colorant and the release agent do not need to be dissolved in the organic solvent, and may be dispersed. When using a colorant and a release agent in a dispersed state, it is preferable to disperse using a disperser such as a bead mill.

(Granulation process)
The granulation step is a step of preparing a dispersion (granulated product) by dispersing the obtained resin composition in an aqueous medium using a dispersant so as to have a predetermined toner particle diameter. As the aqueous medium, water is mainly used. Moreover, it is preferable that the said aqueous medium contains 1 to 30 mass% of monovalent metal salts. By containing the monovalent metal salt, the organic solvent in the resin composition is prevented from diffusing into the aqueous medium, and the crystallinity of the resin contained in the obtained toner particles is increased, thereby increasing the toner content. The blocking property tends to be good and the toner particle size distribution tends to be good.
Examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride, and potassium bromide. Among these, sodium chloride and potassium chloride are preferable.
The mixing ratio (mass ratio) of the aqueous medium and the resin composition is preferably aqueous medium / resin composition = 90/10 to 50/50.

  Although the said dispersing agent is not specifically limited, As an organic type dispersing agent, a surfactant of a cation type, an anion type, and a nonionic type is used, An anion type thing is preferable. Examples thereof include sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfonate, sodium alkyl diphenyl ether disulfonate, and the like. On the other hand, examples of the inorganic dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, and silica powder.

  In the present invention, tricalcium phosphate as an inorganic dispersant is preferred. This is because there is very little adverse effect on the granulating property and its stability, and further on the properties of the obtained toner.

  The amount of dispersant added is determined according to the particle size of the granulated product, and the particle size decreases as the amount of dispersant added increases. Therefore, although the addition amount of a dispersing agent changes with desired particle diameters, it is preferable to use in 0.1-15 mass% with respect to a resin composition. If it is less than 0.1% by mass, coarse powder is likely to be generated, and if it exceeds 15% by mass, unnecessary fine particles are likely to be generated.

Moreover, when preparing the dispersion of a resin composition in an aqueous medium, it is preferable to carry out under high-speed shearing. The dispersion of the resin composition dispersed in the aqueous medium is preferably granulated to have a weight average particle diameter of 10 μm or less, more preferably about 4 to 9 μm.
Various high-speed dispersers and ultrasonic dispersers are examples of devices that apply high-speed shearing.
On the other hand, the weight average particle size of the dispersion can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) by the Coulter method.

(Desolvation process)
In the solvent removal step, the organic solvent is removed from the obtained dispersion. The removal of the organic solvent is preferably performed while stirring. Moreover, the removal rate of an organic solvent can also be controlled by heating and pressure-reducing as needed.

(Washing and drying process)
After the solvent removal step, a washing / drying step of washing the toner particles multiple times with water or the like, and filtering and drying the toner particles may be performed. Further, when a dispersant that dissolves under acidic conditions such as tricalcium phosphate is used as the dispersant, it is preferable to wash with water after washing with hydrochloric acid or the like. By washing, the dispersant used for granulation can be removed, and the toner characteristics can be improved. After washing, the toner can be obtained by filtration and drying. The obtained toner is added with inorganic fine particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin by applying shearing force in a dry state as necessary. Also good. These inorganic fine particles and resin particles function as external additives such as a charging aid, a fluidity aid, and a cleaning aid.

<Emulsion aggregation method>
The emulsion aggregation method is a production method for producing toner particles by preparing in advance a sufficiently fine resin particle dispersion with respect to a target particle size and aggregating the resin particles in an aqueous medium.
In the emulsion aggregation method, toner is manufactured through an emulsification step, an aggregation step, a fusion step, a cooling step, and a washing step of resin fine particles. Hereinafter, the toner production method using the emulsion aggregation method will be specifically described, but the present invention is not limited thereto.

(Emulsification process of resin fine particles)
In the emulsion aggregation method, resin fine particles are first prepared. The resin fine particles can be produced by a known method, but are preferably produced by the following method.
The olefin-based ester group-containing copolymer and the α-olefin copolymer are dissolved in an organic solvent to form a uniform solution. Thereafter, a basic compound and, if necessary, a surfactant are added. Further, an aqueous medium is added to the solution to form fine particles. Finally, it is preferable to prepare a resin fine particle dispersion in which the solvent is removed and the resin fine particles are dispersed. When the resin fine particles are formed by co-emulsification of the olefinic ester group-containing copolymer and the α-olefin copolymer, the olefinic ester group-containing copolymer and the α in the atomized organic phase. -The olefin copolymer is mixed in the fine particles. The compatibility in the toner is increased, and as a result, the storage stability of the toner is increased. More specifically, the olefin ester group-containing copolymer and the α-olefin copolymer are dissolved by heating in an organic solvent, and a surfactant or base is added. Subsequently, a co-emulsion liquid (resin fine particle dispersion) containing a resin is prepared by slowly adding an aqueous medium while applying shear with a homogenizer or the like. Alternatively, a co-emulsion liquid containing a resin is prepared by applying shearing with a homogenizer or the like after adding an aqueous medium. Thereafter, the solvent is removed by heating or decompression to prepare a co-emulsion liquid (resin fine particle dispersion) of resin fine particles.

  The concentration of the resin component dissolved in the organic solvent is preferably 10% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 50% by mass or less with respect to the organic solvent. Any organic solvent can be used as long as it can dissolve the resin, but the solubility in the olefinic ester group-containing copolymer such as toluene, xylene, and ethyl acetate is not limited. Are preferred.

  The surfactant used during the emulsification is not particularly limited. For example, sulfate anion surfactant, sulfonate salt, carboxylate salt, phosphate ester, soap anionic surfactant; amine salt type, quaternary ammonium salt type cationic surfactant, polyethylene glycol type, Examples thereof include alkylphenol ethylene oxide adduct-based and polyhydric alcohol-based nonionic surfactants.

  Examples of the base used during emulsification include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The said base may be used individually by 1 type, and may use 2 or more types together.

  The volume-based median diameter of the resin fine particles is preferably 0.05 to 1.0 μm, and more preferably 0.1 to 0.6 μm. When the median diameter is within the above range, toner particles having a desired particle diameter are easily obtained. The volume-based median diameter can be measured by using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso).

(Aggregation process)
The agglomeration step refers to mixing the colorant fine particle dispersion or the release agent fine particle dispersion with the resin fine particle dispersion described above to prepare a mixed liquid, and then aggregating particles contained in the prepared mixed liquid. And forming an aggregate. As a method for forming an aggregate, for example, a method in which a flocculant is added and mixed in the mixed solution, and the temperature is increased or mechanical power or the like is appropriately added can be suitably exemplified.

  The colorant fine particle dispersion used in the aggregation step is prepared by dispersing the above-described colorant. The colorant fine particles are dispersed by a known method. For example, a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure counter collision type dispersing machine, or the like is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.

  The release agent fine particle dispersion used in the aggregation step is prepared by dispersing the above-described release agent in an aqueous medium. The releasing agent is dispersed by a known method. For example, a media type dispersing machine such as a rotary shearing type homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.

  Examples of the aggregating agent used in the aggregating step include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; trivalent metals such as iron and aluminum; Examples thereof include polyvalent metal salts such as aluminum. From the viewpoint of particle size controllability in the aggregation process, divalent metal salts such as calcium chloride and magnesium sulfate are preferred.

  The addition and mixing of the flocculant is preferably performed in a temperature range from room temperature to 75 ° C. When the mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using a known mixing device, homogenizer, mixer, or the like.

  The average particle diameter of the aggregate formed in the aggregation process is not particularly limited, but it is usually preferable to control the average particle diameter to 4.0 to 7.0 μm so as to be the same as the average particle diameter of the toner particles to be obtained. . Control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method.

(Fusion process)
The fusing step is a step of producing particles in which the agglomerate surface is smoothed by heating and fusing the agglomerates to a temperature equal to or higher than the melting point of the olefinic ester group-containing copolymer. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between toner particles.

  Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, both nitrotriacetate (NTA) salts, COOH and OH There are many water-soluble polymers (polyelectrolytes) that contain the following functionalities.

  The heating temperature ranges from the melting point of the olefin ester group-containing copolymer contained in the aggregate to a temperature at which the olefin ester group-containing copolymer or α-olefin copolymer is thermally decomposed. I just need it. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes to 10 hours.

(Cooling process)
The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the crystallization temperature of the olefinic ester group-containing copolymer. If the cooling is not performed to a temperature lower than the crystallization temperature, coarse particles are generated. A specific cooling rate is 0.1 to 50 ° C./min.

(Washing process)
Impurities in the toner can be removed by repeatedly washing and filtering the particles produced through the above steps. Specifically, the toner is preferably washed with an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, and further washed with pure water. Cleaning with pure water can remove metal salts, surfactants, and the like in the toner by repeating filtration a plurality of times. The number of times of filtration is preferably 3 to 20 times from the viewpoint of production efficiency, and more preferably 3 to 10 times.

(Drying process)
The particles obtained in the above step are dried, and if necessary, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin are sheared in a dry state. You may add by applying force. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.

  Hereinafter, although the present invention is explained still in detail using an example and a comparative example, the mode of the present invention is not limited to these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Production of resin fine particle 1 dispersion>
・ Toluene (Wako Pure Chemical Industries) 300g
Ethylene-vinyl acetate copolymer EVA-A (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 8% by mass, acid value = 0 mgKOH / g, weight average molecular weight: 110000, melt Flow rate: 12 g / 10 min, melting point: 86 ° C., elongation at break = 700%, (l + m + n) /Z1=1.00) 80 g
Ethylene-1-butene copolymer A (R ⁶ = C ₂ H ₅ , unit ratio represented by formula (5): 23% by mass, acid value = 0 mgKOH / g, melting point: 55 ° C., elongation at break = 1000 %, (O + p) /Z2=1.00) 20 g
Olefinic acid group-containing copolymer A (ethylene-methacrylic acid copolymer, melt flow rate: 60 g / 10 min, melting point = 90 ° C., acid value = 90 mgKOH / g) 25 g
The above formulations were mixed and dissolved at 90 ° C.

Separately, 0.7 g of sodium dodecylbenzenesulfonate, 1.5 g of sodium laurate, and 0.8 g of N, N-dimethylaminoethanol were added to 700 g of ion-exchanged water and dissolved by heating at 90 ° C. Next, the toluene solution and the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle 1 dispersion) having a resin fine particle 1 concentration of 20%.
The volume-based median diameter of the resin fine particles 1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

<Production of resin fine particle 2 dispersion>
Resin fine particle 2 dispersion was obtained in the same manner as the resin fine particle 1 dispersion except that 90 g of ethylene-vinyl acetate copolymer EVA-A and 10 g of ethylene-1-butene copolymer A were changed. . The volume-based median diameter of the obtained resin fine particles 2 was 0.48 μm.

<Production of resin fine particle 3 dispersion>
Resin fine particle 3 dispersion was obtained in the same manner as the resin fine particle 1 dispersion except that 70 g of ethylene-vinyl acetate copolymer EVA-A and 30 g of ethylene-1-butene copolymer A were changed. . The volume-based median diameter of the obtained resin fine particles 3 was 0.33 μm.

<Production of resin fine particle 4 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate copolymer EVA-B (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 10% by mass, acid value = 0 mgKOH. / G, melt flow rate: 14 g / 10 min, melting point: 75 ° C., elongation at break = 800%, (l + m + n) /Z1=1.00) Thus, a resin fine particle 4 dispersion was obtained. The obtained resin fine particles 4 had a volume-based median diameter of 0.45 μm.

<Production of resin fine particle 5 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate copolymer EVA-C (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 14% by mass, acid value = 0 mgKOH. / G, melt flow rate: 20 g / 10 min, melting point: 69 ° C., elongation at break = 800%, (l + m + n) /Z1=1.00) Thus, a resin fine particle 5 dispersion was obtained. The obtained resin fine particles 5 had a volume-based median diameter of 0.45 μm.

<Production of resin fine particle 6 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate copolymer EVA-D (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 3% by mass, acid value = 0 mgKOH. / G, melt flow rate: 75 g / 10 min, melting point: 96 ° C., elongation at break = 460%, (l + m + n) /Z1=1.00) A resin fine particle 6 dispersion was obtained. The obtained resin fine particle 6 had a volume-based median diameter of 0.45 μm.

<Production of resin fine particle 7 dispersion>
Ethylene-1-butene copolymer A is converted to ethylene-1-butene copolymer B (R ⁶ = C ₂ H ₅ , unit ratio represented by formula (5): 14% by mass, acid value = 0 mgKOH / g, melting point : Resin fine particle 7 dispersion was obtained in the same manner as in the production method of resin fine particle 1 dispersion, except that the temperature was changed to 94 ° C., elongation at break = 900%, (o + p) /Z2=1.00). The volume-based median diameter of the obtained resin fine particles 7 was 0.45 μm.

<Production of resin fine particle 8 dispersion>
The ethylene-1-butene copolymer A is converted to an ethylene-1-octene copolymer C (R ⁶ = C ₆ H ₁₃ , unit ratio represented by the formula (5): 23% by mass, acid value = 0 mgKOH / g, melting point : Resin fine particle 8 dispersion was obtained in the same manner as in the production method of resin fine particle 1 dispersion except that the temperature was changed to 76 ° C., elongation at break = 700%, (o + p) /Z2=1.00). The volume-based median diameter of the obtained resin fine particles 8 was 0.52 μm.

<Production of resin fine particle 9 dispersion>
Ethylene-1-butene copolymer A is converted to ethylene-1-octene copolymer D (R ⁶ = C ₆ H ₁₃ , unit ratio represented by formula (5): 38% by mass, acid value = 0 mgKOH / g, melting point : Resin fine particle 9 dispersion was obtained in the same manner as in the production method of resin fine particle 1 dispersion, except that the temperature was changed to 65 ° C., elongation at break = 800%, (o + p) /Z2=1.00). The volume-based median diameter of the obtained resin fine particles 9 was 0.46 μm.

<Production of resin fine particle 10 dispersion>
・ Toluene (Wako Pure Chemical Industries) 300g
Ethylene-vinyl acetate copolymer EVA-E (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 10% by mass, acid value = 0 mgKOH / g, melt flow rate: 200 g / 10 Min, melting point: 75 ° C., elongation at break = 210%, (l + m + n) /Z1=1.00) 80 g
Ethylene-1-butene copolymer A (R ⁶ = C ₂ H ₅ , unit ratio represented by formula (2): 23% by mass, acid value = 0 mgKOH / g, melting point: 55 ° C., elongation at break = 1000 %, (O + p) /Z2=1.00) 20 g
The above formulations were mixed and dissolved at 90 ° C.

  Separately, 5 g of sodium dodecylbenzenesulfonate and 10 g of sodium laurate were added to 700 g of ion-exchanged water and dissolved by heating at 90 ° C. Next, the toluene solution and the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle 10 dispersion) having a concentration of resin fine particles 1 of 20%. The volume-based median diameter of the obtained resin fine particles 10 was 0.22 μm.

<Production of resin fine particle 11 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-ethyl acrylate copolymer EEA-A (R ¹ = H, R ⁴ = H, R ⁵ = C ₂ H ₅ , ester group concentration: 11% by mass, acid. Value = 0 mg KOH / g, melt flow rate: 20 g / 10 min, melting point: 91 ° C., elongation at break = 900%, (l + m + n) /Z1=1.00) Similarly, a resin fine particle 11 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles 11 was 0.41 μm.

<Production of resin fine particle 12 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-methyl acrylate copolymer EMA-A (R ¹ = H, R ⁴ = H, R ⁵ = CH ₃ , ester group concentration: 7% by mass, acid value = 0 mg KOH / g, melt flow rate: 14 g / 10 min, melting point: 87 ° C., elongation at break = 800%, (l + m + n) /Z1=1.00) A resin fine particle 12 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles 12 was 0.46 μm.

<Production of resin fine particle 13 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-methyl methacrylate copolymer EMMA-A (R ¹ = H, R ⁴ = CH ₃ , R ⁵ = CH ₃ , ester group concentration: 8% by mass, acid value = 0 mg KOH / g, melt flow rate: 7 g / 10 min, melting point: 89 ° C., elongation at break = 750%, (l + m + n) /Z1=1.00) Similarly, a resin fine particle 13 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles 13 was 0.44 μm.

<Production of resin fine particle 14 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate-vinyl valerate copolymer EVA-F (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 7% by mass, Unit derived from vinyl valerate (formula (4)) ratio: 6% by mass, acid value = 0 mgKOH / g, melt flow rate: 14 g / 10 min, melting point: 83 ° C., elongation at break = 750%, (l + m + n) /Z1=0.94) A resin fine particle 14 dispersion was obtained in the same manner as in the production method of the resin fine particle 1 dispersion. The volume-based median diameter of the obtained resin fine particles 14 was 0.42 μm.

<Production of resin fine particle 15 dispersion>
Ethylene-1-butene copolymer A is converted to ethylene-1-butene copolymer E (R ⁶ = C ₂ H ₅ , unit ratio represented by formula (5): 8% by mass, acid value = 0 mgKOH / g, melting point A resin fine particle 15 dispersion was obtained in the same manner as the production method of the resin fine particle 10 dispersion, except that it was changed to 154 ° C., elongation at break = 900%, (o + p) /Z2=1.00). The volume-based median diameter of the obtained resin fine particles 15 was 0.68 μm.

<Production of resin fine particle 16 dispersion>
Ethylene-1-butene copolymer A is converted to ethylene-1-octene copolymer F (R ⁶ = C ₆ H ₁₃ , unit ratio represented by formula (5): 57% by mass, acid value = 0 mgKOH / g, melting point : Resin fine particle 16 dispersion was obtained in the same manner as in the production method of Resin fine particle 10 dispersion, except that it was changed to 56 ° C., elongation at break = 700%, (o + p) /Z2=1.00). The obtained resin fine particles 16 had a volume-based median diameter of 0.32 μm.

<Production of resin fine particle 17 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate copolymer EVA-G (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 1% by mass, acid value = 0 mgKOH. / G, melt flow rate: 3 g / 10 min, melting point: 105 ° C., elongation at break = 600%, (l + m + n) /Z1=1.00) Thus, a resin fine particle 17 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles 17 was 5.45 μm.

<Production of resin fine particle 18 dispersion>
Ethylene-vinyl acetate copolymer EVA-A was converted to ethylene-vinyl acetate copolymer EVA-H (R ¹ = H, R ² = H, R ³ = CH ₃ , ester group concentration: 21% by mass, acid value = 0 mgKOH. / G, melt flow rate: 2 g / 10 min, melting point: 40 ° C., elongation at break = 870%, (l + m + n) /Z1=1.00) Thus, a resin fine particle 18 dispersion was obtained. The obtained resin fine particles 18 had a volume-based median diameter of 6.81 μm.

<Production of resin fine particle 19 dispersion>
A resin fine particle 19 dispersion was obtained in the same manner as the production method of the resin fine particle 10 dispersion except that the ethylene-1-butene copolymer A was not used. The volume-based median diameter of the obtained resin fine particles 19 was 5.51 μm.

<Production of resin fine particle 20 dispersion>
Ethylene-vinyl acetate copolymer EVA-A is converted into polyester resin A [composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100. : 50:50], number average molecular weight (Mn) = 4,600, weight average molecular weight (Mw) = 16,500, peak molecular weight (Mp) = 10,400, glass transition temperature (Tg) = 70 ° C, acid value = 13 mg KOH / g], and a resin fine particle 20 dispersion was obtained in the same manner as in the production method of the resin fine particle 10 dispersion except that 1.6 g of N, N-dimethylaminoethanol was added together with ion-exchanged water. The obtained resin fine particle 20 had a volume-based median diameter of 0.22 μm.

<Production of resin fine particle 21 dispersion>
Without using ethylene-vinyl acetate copolymer EVA-A and ethylene-1-butene copolymer A, crystalline polyester resin A (composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100 ], Number average molecular weight (Mn) = 5,500, weight average molecular weight (Mw) = 15,500, peak molecular weight (Mp) = 11,400, melting point = 72 ° C., acid value = 13 mgKOH / g) A resin fine particle 21 dispersion was obtained in the same manner as the production method of the resin fine particle 10 dispersion except that the amount was 100 g and 2.1 g of N, N-dimethylaminoethanol was added together with ion-exchanged water. The volume-based median diameter of the obtained resin fine particles 21 was 0.25 μm.

<Manufacture of colorant fine particle dispersion>
Coloring agent 10.0 parts by mass (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.5 parts by mass Was used for about 1 hour to prepare an aqueous dispersion (colorant fine particle dispersion) having a colorant fine particle concentration of 10%. The volume-based median diameter of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.20 μm.

<Manufacture of aliphatic hydrocarbon compound fine particle dispersion>
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa) 20.0 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.0 part by mass 79.0 parts by mass The above was put into a mixing vessel equipped with a stirrer, and then heated to 90 ° C. and circulated to Claremix W Motion (manufactured by M Technique) for 60 minutes. The conditions for distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the system is cooled to 40 ° C. under the cooling treatment conditions of a rotor rotational speed of 1000 r / min, a screen rotational speed of 0 r / min, and a cooling rate of 10 ° C./min. A dispersion (aliphatic hydrocarbon compound fine particle dispersion) was obtained. The volume distribution standard 50% particle size (d50) of the aliphatic hydrocarbon compound fine particles was measured using a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

<Manufacture of silicone oil emulsion>
・ Silicone oil 20.0 parts by mass (Dimethyl silicone oil Shin-Etsu Chemical: KF96-50CS)
-Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.0 part by mass-79.0 parts by mass of ion-exchanged water An aqueous dispersion having a silicone oil concentration of 20% was prepared by dispersing the silicone oil for about 1 hour. The volume-based median diameter of the silicone oil particles in the obtained silicone oil emulsion was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and found to be 0.09 μm.

<Example 1>
・ Resin fine particle 1 dispersion 500g
・ Colorant fine particle dispersion 80g
-Aliphatic hydrocarbon compound fine particle dispersion 150g
・ Silicone oil emulsion 50g
・ Ion exchange water 160g
The above materials were put into a round stainless steel flask and mixed, and then 60 g of a 10% magnesium sulfate aqueous solution was added. Subsequently, the mixture was dispersed for 10 minutes at 5000 r / min using a homogenizer (manufactured by IKA: Ultra Tarrax T50). Thereafter, the mixture was heated to 73 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixture was stirred. After maintaining at 73 ° C. for 20 minutes, the volume average particle diameter of the formed aggregated particles was confirmed to be formed by using Coulter Multisizer III, and aggregated particles having a volume average particle diameter of about 6.0 μm were formed. It was.

  After adding 330 g of 5% ethylenediamine tetraacetate aqueous solution to the dispersion of the aggregated particles, the mixture was heated to 98 ° C. while stirring was continued. And the aggregated particle was united by hold | maintaining at 98 degreeC for 1 hour.

  Then, it cooled to 50 degreeC and accelerated | stimulated crystallization of the ethylene-vinyl acetate copolymer by hold | maintaining for 3 hours. Then, after cooling to 25 degree | times and filtering and solid-liquid separation, the filtrate was wash | cleaned with 0.5% ethylenediamine tetraacetate aqueous solution, and also wash | cleaned with ion-exchange water. The toner particles having a volume-based median diameter of 5.4 μm were obtained by drying using a vacuum dryer after the washing.

  With respect to 100 parts by mass of the obtained toner particles, 1.5 parts by mass of hydrophobized silica fine powder having a primary particle size of 10 nm and 2.5 g of hydrophobized silica fine powder having a primary particle size of 100 nm Toner 1 was obtained by dry mixing the mass parts with a Henschel mixer (Mitsui Mine). Table 1 shows the constituent conditions of the obtained toner 1.

<Example 2>
A toner 2 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 2. The volume-based median diameter of the obtained toner 2 was 5.3 μm.

<Example 3>
A toner 3 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 3. The obtained toner 3 had a volume-based median diameter of 5.3 μm.

<Example 4>
A toner 4 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 4. The obtained toner 4 had a volume-based median diameter of 5.2 μm.

<Example 5>
A toner 5 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 5. The obtained toner 5 had a volume-based median diameter of 5.5 μm.

<Example 6>
A toner 6 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 6. The obtained toner 6 had a volume-based median diameter of 5.2 μm.

<Example 7>
A toner 7 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 7. The toner 7 thus obtained had a volume-based median diameter of 5.1 μm.

<Example 8>
A toner 8 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 8. The obtained toner 8 had a volume-based median diameter of 5.1 μm.

<Example 9>
A toner 9 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 9. The obtained toner 9 had a volume-based median diameter of 5.4 μm.

<Example 10>
A toner 10 was obtained in the same manner as in Example 1 except that the addition amount of the aliphatic hydrocarbon compound fine particle dispersion was changed to 50 g. The toner 10 thus obtained had a volume-based median diameter of 5.2 μm.

<Example 11>
Toner 11 was obtained in the same manner as in Example 1 except that the amount of the silicone oil emulsion added was 100 g. The resulting toner 11 had a volume-based median diameter of 5.1 μm.

<Example 12>
A toner 12 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 10. The volume-based median diameter of the obtained toner 12 was 5.2 μm.

<Example 13>
Toner 13 was obtained in the same manner as in Example 1 except that 500 g of resin fine particle 1 dispersion was changed to 375 g of resin fine particle 1 dispersion and 125 g of resin fine particle 21 dispersion. The volume-based median diameter of the obtained toner 13 was 6.1 μm.

<Example 14>
A toner 14 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 11. The toner 14 thus obtained had a volume-based median diameter of 5.2 μm.

<Example 15>
A toner 15 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 12. The obtained toner 15 had a volume-based median diameter of 5.1 μm.

<Example 16>
A toner 16 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 13. The toner 16 thus obtained had a volume-based median diameter of 5.1 μm.

<Example 17>
Toner 17 was obtained in the same manner as in Example 1 except that 500 g of resin fine particle 1 dispersion was changed to 250 g of resin fine particle 1 dispersion and 250 g of resin fine particle 11 dispersion. The toner 17 thus obtained had a volume-based median diameter of 5.0 μm.

<Example 18>
A toner 18 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 14. The obtained toner 18 had a volume-based median diameter of 5.2 μm.

<Example 19>
A toner 19 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 15. The obtained toner 19 had a volume-based median diameter of 5.1 μm.

<Example 20>
A toner 20 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 16. The resulting toner 20 had a volume-based median diameter of 5.3 μm.

<Comparative Example 1>
A comparative toner 1 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to the resin fine particles 17. The volume-based median diameter of the obtained comparative toner 1 was 11.6 μm.

<Comparative example 2>
A comparative toner 2 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 18. The volume-based median diameter of the obtained comparative toner 2 is. It was 10.4 μm.

<Comparative Example 3>
A comparative toner 3 was obtained in the same manner as in Example 1 except that the resin fine particles 1 were changed to resin fine particles 19. The volume-based median diameter of the obtained comparative toner 3 was 10.3 μm.

<Comparative Example 4>
Example 1 except that the resin fine particle 1 is the resin fine particle 20, the addition amount of the aliphatic hydrocarbon compound fine particle dispersion is 50 g, the silicone oil emulsion is not used, and the temperature of the aggregation process is 60 ° C. Thus, Comparative Toner 4 was obtained. The volume-based median diameter of the obtained comparative toner 4 was 5.4 μm.

<Comparative Example 5>
Example 1 except that the resin fine particles 1 are resin fine particles 21, the addition amount of the aliphatic hydrocarbon compound fine particle dispersion is 50 g, no silicone oil emulsion is used, and the temperature of the aggregation process is 60 ° C. Thus, Comparative Toner 5 was obtained. The volume-based median diameter of the obtained comparative toner 5 was 5.4 μm.

The following evaluation tests were conducted using the toners. The evaluation results are shown in Table 2.
<Evaluation of low-temperature fixability before storage>
The toner and a ferrite carrier surface-coated with a silicone resin (average particle size 42 μm) were mixed so that the toner concentration was 8% by mass to prepare a two-component developer. A commercially available full color digital copying machine (CLC1100, manufactured by Canon Inc.) was used to form an unfixed toner image (0.6 mg / cm ² ) on image receiving paper (64 g / m ² ). A fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon) was remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. Under normal temperature and normal humidity, the process speed was set to 246 mm / second, and the state when the unfixed image was fixed was visually observed and evaluated as follows.
A: Fixing was possible at a temperature of 120 ° C. or lower.
B: Fixing was possible at a temperature higher than 120 ° C. and 140 ° C. or lower.
C: Fixing was possible at a temperature higher than 140 ° C. and not higher than 200 ° C., or there was no temperature range where fixing was possible.

<Evaluation of low-temperature fixability after storage>
The toner is allowed to stand in a high-temperature and high-humidity tank at 50 ° C. and a humidity of 50% for 3 days, and the recovered toner is subjected to low-temperature fixability after storage in the same manner as in the low-temperature fixability evaluation test before storage. evaluated.

<Evaluation of eraser resistance>
The toner is fixed by the same method as the low temperature fixability evaluation test method, and the fixed material at the highest fixable temperature is erased (product name: MONO, manufactured by Dragonfly Pencil Co., Ltd.) three times with a load of 300 g. By rubbing, the erasure resistance of the fixed image was tested and evaluated as follows.
A: The fixed image was not erased by the eraser.
B: The density of the fixed image was lowered by erasing with an eraser.
C: The fixed image was erased with an eraser.

<Evaluation of charge retention>
0.01 g of toner was weighed into an aluminum pan and charged to −600 V using a strocolon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface potentiometer (model 347 manufactured by Trek Japan) in an atmosphere of 30 ° C. and 80% humidity. From the measurement results, the charge retention rate was calculated from the following formula and evaluated as follows.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) × 100
A: Charge retention is 90% or more B: Charge retention is 50% or more and less than 90% C: Charge retention is 10% or more and less than 50% D: Charge retention is less than 10%

Claims (12)

A toner having toner particles containing a resin component,
The resin component has an olefin ester group-containing copolymer and an α-olefin copolymer as a binder resin,
The olefin ester group-containing copolymer is a unit Y1 represented by the following formula (1):
Having at least one unit Y2 selected from the group of unit Y2-1 represented by the following formula (2) and unit Y2-2 represented by the following formula (3),
The ester group concentration is 2% by mass or more and 18% by mass or less with respect to the total mass of the olefinic ester group-containing copolymer,
The α-olefin copolymer is
A unit Y3 represented by the following formula (4);
It has unit Y4 shown by the following formula (5),
The content of the unit Y4 is 5% by mass or more and 50% by mass or less with respect to the total mass of the α-olefin copolymer,
Having a crystallinity of a melting point of 50 ° C. or higher and 100 ° C. or lower,
A toner in which the content of the olefinic ester group-containing copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component.

Wherein R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is CH ₃ or C ₂ H ₅ , R ⁴ is H or CH ₃ , R ⁵ is CH ₃ or C ₂ H ₅ and R ⁶ is CnH2n + 1 (n is an integer of 2 or more and 6 or less).   2. The toner according to claim 1, wherein the content of the α-olefin copolymer contained in the resin component is 5% by mass or more and 40% by mass or less based on the total mass of the resin component. The endothermic amount W1 obtained by measurement using a differential scanning calorimeter (DSC) of the olefin ester group-containing copolymer and the differential scanning calorimeter (DSC) of the α-olefin copolymer are measured. The endothermic amount W2 obtained, the endothermic amount Wn of other crystalline components contained in the toner, and the endothermic amount Wt obtained by measuring using the differential scanning calorimeter (DSC) of the toner are as follows: The toner according to claim 1, wherein the toner satisfies the following condition.
0.4 ≦ Wt / (W1 + W2 + Wn) ≦ 0.8   The total mass of the olefin ester group-containing copolymer is Z1, the unit Y1 represented by the formula (1), the unit Y2-1 represented by the formula (2), and the unit Y2- represented by the formula (3). 2. The value of (l + m + n) / Z1 of the olefinic ester group-containing copolymer contained in the resin component is 0.80 or more, where 1 is 1, m, and n, respectively. 4. The toner according to any one of items 1 to 3.   When the total mass of the α-olefin copolymer is Z2, the mass of each of the unit Y3 represented by the formula (4) and the unit Y4 represented by the formula (5) is o and p, the resin component contains The toner according to claim 1, wherein the α-olefin copolymer contained has a value of (o + p) / Z2 of 0.80 or more.   The toner according to claim 1, wherein the olefin ester group-containing copolymer is an ethylene-vinyl acetate copolymer.   The toner according to claim 1, wherein the α-olefin copolymer is a random copolymer of ethylene and 1-butene.   The toner according to claim 1, wherein the toner contains an olefinic acid group-containing copolymer having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less.   The toner according to any one of claims 1 to 8, wherein the olefin-based ester group-containing copolymer has a melt flow rate of 5 g / 10 min or more and 30 g / 10 min or less.   The toner contains an aliphatic hydrocarbon compound having a melting point of 50 ° C. or higher and 100 ° C. or lower, and the aliphatic hydrocarbon compound is 1 part by weight or more and 40 parts by weight with respect to 100 parts by weight of the binder resin. The toner according to any one of claims 1 to 9, which is contained below.   The proportion of the unit Y2-1 represented by the formula (2) of the olefinic ester group-containing copolymer is 5% by mass or more and 20% by mass or less with respect to the total mass of the olefinic ester group-containing copolymer. The toner according to claim 1.   12. The toner according to claim 1, wherein the toner contains silicone oil, and the silicone oil is contained in an amount of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the binder resin. The toner described.