JP2018041069A - Toner and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability, charge retentivity, and hot offset resistance, and a method for manufacturing the toner.SOLUTION: A toner includes toner particles containing a resin component. The resin component includes an ester group-containing olefin copolymer and a crosslinked body of an aliphatic hydrocarbon resin having an unsaturated bond; the copolymer includes a monomer unit represented by a specific structure; the content of the copolymer is 50 mass% or more based on the total mass of the resin component.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system and a toner manufacturing method.

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 of the toner, there has been proposed a technique using a crystalline polyester resin having a sharp melt property in which the viscosity greatly decreases 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 4). 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 is used as a resin for an electrophotographic toner, it exhibits excellent low-temperature fixability and high-temperature storage properties 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 a monomer unit derived from an olefinic compound such as ethylene or propylene as a resin having a high volume resistance and a glass transition temperature of room temperature or lower.
Specifically, ethylene (propylene) -acetate copolymer such as ethylene-vinyl acetate copolymer; ethylene (propylene) -acrylate ester copolymer such as ethylene-methyl acrylate copolymer. Polymer: An ethylene (propylene) -methacrylic acid ester copolymer such as ethylene-methyl methacrylate copolymer was used to try to achieve both low-temperature fixability and charge retention.
However, it is difficult to satisfy the low-temperature fixability under high-speed conditions only by partially including these ester group-containing olefin copolymers in the toner as proposed in Patent Documents 4 to 8. It was.
On the other hand, as described in Patent Documents 9 and 10, when these ester group-containing olefin copolymers are used as the main resin of the toner, there is a problem that the hot offset resistance is lowered.
In recent years, there has been a demand for multimedia compatibility that can support various recording materials (media) such as postcards, small-size paper, envelopes, cardboard, and label paper. However, when recording materials of different sizes pass over the fixing member continuously, if the recording material with a small size passes over the fixing member first, the portion of the fixing member on which the recording material does not pass. The temperature rises excessively. Thereafter, when the large recording material passes over the fixing member, the toner on the large recording material is excessively heated, and hot offset tends to occur. Therefore, even when various recording materials are used, it is required to improve hot offset resistance while maintaining low-temperature fixability.
In order to improve the hot offset resistance, the present inventors tried to use a commonly known high molecular weight resin. However, because the ester group-containing olefin copolymer has low polarity and low intermolecular force, it is resistant to hot offset even when a high molecular weight resin of the ester group-containing olefin copolymer is used in combination. Could not be improved.
An object of the present invention is to provide a toner excellent in low-temperature fixability, charge retention, and hot offset resistance, and a method for producing the toner.

As a result of intensive studies by the present inventors, ethylene (propylene) -acetate copolymer such as ethylene-vinyl acetate copolymer; ethylene (propylene) -acrylate ester such as ethylene-methyl acrylate Copolymers: ethylene (propylene) -methacrylic acid ester copolymers such as ethylene-methyl methacrylate or a mixture thereof, and a cross-linked aliphatic hydrocarbon resin having an unsaturated bond Thus, it was revealed that a toner excellent in low-temperature fixing property, charge holding property, and hot offset resistance can be obtained.
Since the copolymer has a high crystallinity despite a low glass transition temperature, it has good blocking resistance at high temperatures. However, when other resin components are added and dissolved, the degree of crystallinity is lowered and the blocking resistance is lowered.
However, a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond does not impair the crystallization of the copolymer due to the similarity of the chemical structure, and does not lower the blocking resistance.
Furthermore, it quickly dissolves in the copolymer at the fixing temperature of the toner, spreads in the toner, and the hot offset resistance is remarkably improved by the entanglement effect of molecular chains due to the cross-linked structure.

That is, the present invention
A toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the following formula (1);
Having at least one monomer unit Y2 selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3);
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
The toner is characterized in that the content of the monomer unit Y2 is 3% by mass or more and 35% by mass or less with respect to the total mass of the ester group-containing olefin copolymer.
The present invention also provides:
A method for producing a toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
A preparation step of preparing a resin fine particle dispersion in which the resin fine particles for producing the resin component are dispersed in an aqueous medium; and
A crosslinking step of crosslinking the aliphatic hydrocarbon resin having an unsaturated bond present in the resin fine particles using a crosslinking agent;
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the following formula (1);
Having at least one monomer unit Y2 selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3);
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
In the toner production method, the content of the monomer unit Y2 is 3% by mass or more and 35% by mass or less based on the total mass of the ester group-containing olefin copolymer.

（前記式（１）〜（３）中、Ｒ^１はＨ又はＣＨ_３を示し、Ｒ^２はＨ又はＣＨ_３を示し、Ｒ^３はＣＨ_３又はＣ_２Ｈ_５を示し、Ｒ^４はＨ又はＣＨ_３を示し、Ｒ^５はＣＨ_３又はＣ_２Ｈ_５を示す。）

(In the formulas (1) to (3), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or CH ₃ represents R ⁵ represents CH ₃ or C ₂ H ₅

  According to the present invention, it is possible to provide a toner excellent in low-temperature fixability, charge retention, and hot offset resistance, and a method for producing the toner.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
Moreover, a monomer unit means the form which the monomer substance in a polymer or resin reacted.
The crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).
The toner of the present invention is a toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the following formula (1);
Having at least one monomer unit Y2 selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3);
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
Content of this monomer unit Y2 is 3 to 35 mass% with respect to the total mass of this ester group containing olefin type copolymer, It is characterized by the above-mentioned.

The resin component refers to a polymer component that mainly contributes to fixing performance.
The resin component includes an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond.
The ester group-containing olefin copolymer is a polymer in which a monomer unit having an ester group is introduced into a polyolefin skeleton by means of copolymerization or the like.
Specifically, at least one selected from the group consisting of a monomer unit Y1 represented by the following formula (1), a monomer unit represented by the following formula (2), and a monomer unit represented by the following formula (3): And a monomer unit Y2.

（前記式（１）〜（３）中、Ｒ^１はＨ又はＣＨ_３を示し、Ｒ^２はＨ又はＣＨ_３を示し、Ｒ^３はＣＨ_３又はＣ_２Ｈ_５を示し、Ｒ^４はＨ又はＣＨ_３を示し、Ｒ^５はＣＨ_３又はＣ_２Ｈ_５を示す。）

(In the formulas (1) to (3), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or CH ₃ represents R ⁵ represents CH ₃ or C ₂ H ₅

Hereinafter, the ester group-containing olefin copolymer will be specifically described.
Specific examples of the ester group-containing olefin copolymer include ethylene-vinyl acetate copolymers in which R ¹ is H, R ² is H, and R ³ is CH ₃ in the above formula.
The ethylene-vinyl acetate copolymer is preferable from the viewpoint of low-temperature fixability because it can be designed to have a low melting point.
Further, an ethylene-methyl acrylate copolymer in which R ¹ in the above formula is H, R ⁴ is H, and R ⁵ is CH ₃ ; in the above formula, R ¹ is H, R ⁴ is H, R ⁵ is An ethylene-ethyl acrylate copolymer that is C ₂ H ₅ ; an ethylene-methyl methacrylate copolymer in which R ¹ is H, R ⁴ is CH ₃ , R ⁵ is CH ₃ in the above formula, Since chemical stability is high, it is preferable from the viewpoint of storage stability in a high temperature and high humidity environment.
The ester group-containing olefin copolymer can be contained in the resin component in one or more kinds.

Further, the total mass of the ester group-containing olefin copolymer is W,
Let the mass of the monomer unit represented by formula (1) be l,
The mass of the monomer unit represented by the formula (2) is m,
When the mass of the monomer unit represented by the formula (3) is n,
From the viewpoint of charge retention and blocking resistance, the value of (l + m + n) / W in the ester group-containing olefin copolymer contained in the resin component is preferably 0.80 or more, and 0.95 or more. More preferably, it is more preferably 1.00.
The ester group-containing olefin copolymer may contain a monomer unit other than the monomer unit Y1 and the monomer unit Y2. Although it will not specifically limit unless the effect of this invention is impaired, For example, the monomer unit shown by following formula (4) and the vinyl-type monomer unit shown by Formula (5) are mentioned.
These are introduced by adding a corresponding monomer in the copolymerization reaction for producing an ester group-containing olefin copolymer or by modifying the ester group-containing olefin copolymer by a polymer reaction. Can do.

  From the viewpoint of charge retention, the acid value of the ester group-containing olefin copolymer is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and substantially 0 mgKOH / g. Is more preferable.

From the viewpoint of low-temperature fixability, the content of the ester group-containing olefin copolymer in the resin component is 50% by mass or more, preferably 70% by mass or more, based on the total mass of the resin component.
Since the glass transition temperature of the ester group-containing olefin copolymer is 0 ° C. or less, the low-temperature fixability is improved when the content in the resin component is 50% by mass or more.
From the viewpoint of charge retention and low-temperature fixability, the content of the monomer unit Y2 is 3% by mass or more and 35% by mass or less, and 5% by mass or more and 20% by mass with respect to the total mass of the ester group-containing olefin copolymer. It is preferable that it is below mass%.
When the content of the monomer unit Y2 is 35% by mass or less, charge retention as a toner is improved. On the other hand, when the content of the monomer unit Y2 is 3% by mass or more, the adhesion to paper is improved and the low-temperature fixability is improved.

The masses [l], [m], and [n] of the monomer units represented by the above formulas and the content of the monomer unit Y2 can be measured using a general analytical method.
For example, nuclear magnetic resonance (NMR) or pyrolysis gas chromatography may be used.
Hereinafter, a measurement method using ¹ H-NMR will be described.
For example, the hydrogen atom of the monomer unit represented by the formula (1), the hydrogen atom of the acetyl group of the monomer unit represented by the formula (2), the hydrogen atom of the methyl group bonded to the oxygen of the monomer unit represented by the formula (3) By comparing the integral ratios, the content ratio of each monomer unit can be calculated.
Specifically, the content ratio of each monomer unit in the ethylene-vinyl acetate copolymer (monomer unit ratio derived from vinyl acetate: 15% by mass) is calculated by the following method.
A solution in which about 5 mg of a sample is dissolved in 0.5 mL of heavy acetone containing tetramethylsilane as an internal standard of 0.00 ppm is put in a sample tube, and the repetition time is 2.7 seconds, and the number of integration is ¹ H under the conditions of 16 times. -Measure NMR spectra.
The peak of 1.14 to 1.36 ppm corresponds to CH ₂ —CH ₂ of the monomer unit derived from ethylene, and the peak near 2.04 ppm corresponds to CH ₃ of the monomer unit derived from vinyl acetate. The ratio of the integrated values of those peaks is calculated to calculate the content ratio of each monomer unit.

The ester group-containing olefin copolymer is an ester group-containing olefin copolymer A having a softening point of 120 ° C. or higher and 160 ° C. or lower, and an ester group-containing olefin system having a softening point of 70 ° C. or higher and 100 ° C. or lower. It is preferable to contain the copolymer B.
From the viewpoint of enduring impact and pressure when using the toner, it is preferable to contain an ester group-containing olefin copolymer A having a softening point of 120 ° C. or higher and 160 ° C. or lower.
Moreover, it is preferable to contain the ester group containing olefin copolymer B which has a softening point of 70 degreeC or more and 100 degrees C or less from a viewpoint of the glossiness of an image.
From the viewpoint of enduring impact and pressure when using the toner, the content of the ester group-containing olefin copolymer A is preferably 40% by mass or more and 80% by mass or less based on the total mass of the resin component. More preferably, it is 40 mass% or more and 60 mass% or less.
On the other hand, from the viewpoint of glossiness of the image, the content of the ester group-containing olefin copolymer B is preferably 10% by mass or more and 30% by mass or less, and 20% by mass with respect to the total mass of the resin component. % To 30% by mass is more preferable.
The softening point (Tm) can be controlled by changing the molecular weight of the ester group-containing olefin copolymer, and the softening point can be increased by increasing the molecular weight.

In the present invention, the softening point (Tm) is measured according to a manual attached to the apparatus using a load extrusion type capillary rheometer “Flow Characteristics Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation).
In this equipment, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is melted while raising the temperature, and the measurement sample melted is extruded from the die at the bottom of the cylinder. A flow curve can be graphed from (mm) and temperature (° C.).
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 descent amount (outflow end point, Smax) when the outflow is completed and the piston descent amount (lowest point, Smin) when the outflow starts is obtained. (This is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is the sum of X and Smin in the flow curve is defined as the melting temperature in the 1/2 method.
For measurement, a 1.2 g sample was compression molded at 10 MPa for 60 seconds in a 25 ° C. environment using a tablet molding compressor (for example, a standard manual Newton press NT-100H, manufactured by NPA Corporation). And a cylindrical shape having a diameter of 8 mm is used.
The specific operation in the measurement is performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 60 ° 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): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

The breaking elongation of the ester group-containing olefin copolymer is preferably 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 upper limit of the breaking elongation is about 1000% or less.
The breaking elongation is measured under conditions based on JIS K 7162.
When a plurality of ester group-containing olefin copolymers are contained in the resin component, measurement is performed under the above conditions after melt mixing.

The resin component contains a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond.
The aliphatic hydrocarbon resin having an unsaturated bond is not particularly limited as long as it is an aliphatic hydrocarbon resin having a double bond or a triple bond between carbon and carbon in the resin skeleton.
Because of the large number of unsaturated bond sites and the tendency of the crosslinking reaction to proceed, the weight of diene having 4 to 10 carbon atoms such as polybutadiene, polydicyclopentadiene, 1,4-poly (1-propylbuta-1,3-diene), etc. Coalescence is preferred.
Among these, polybutadiene has higher reactivity and remarkably improves the hot offset resistance of the toner.
In addition, since polybutadiene has a resin skeleton similar to that of the ester group-containing olefin copolymer, it is difficult to inhibit crystallization of the ester group-containing olefin copolymer and the blocking resistance is improved.
The weight average molecular weight of the aliphatic hydrocarbon resin having an unsaturated bond (for example, polybutadiene) is preferably 10,000 or more and 300,000 or less, and more preferably 100,000 or more and 300,000 or less.
When the weight average molecular weight is 10,000 or more, the blocking resistance of the toner is further improved, and when it is 300,000 or less, the reactivity of the crosslinking reaction is further increased.

The weight average molecular weight of the aliphatic hydrocarbon resin having an unsaturated bond is determined as a standard polystyrene equivalent molecular weight using gel permeation chromatography (GPC).
The measuring apparatus and conditions are as follows.
・ Device: GPC device “GPC8020” manufactured by Tosoh Corporation
Separation column: “TSKgel G4000HXL” manufactured by Tosoh Corporation
Detector: “RI-8020” manufactured by Tosoh Corporation
・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 1.0 mL / min ・ Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C

Examples of the structure constituting the polybutadiene include a cis-1,4-polybutadiene structure, a trans-1,4-polybutadiene structure, and a 1,2-polybutadiene structure.
In addition, the 1,2-polybutadiene structure is a 1,2-atactic structure in which different isomers are randomly linked as stereoisomers, a 1,2-isotactic structure in which the same isomers are linked, and different isomers alternately. Examples include 1,2-syndiotactic structures in which the bodies are connected.
The polybutadiene may contain other monomer units as required, but it has a 1,2-polybutadiene structure, and a part of it forms a syndiotactic structure to provide crystallinity. It is preferable to have. By having crystallinity, the preservability at high temperature becomes better without disturbing the crystallinity of the ester group-containing olefin copolymer.
From the viewpoint of crystallinity, the content of the 1,2-polybutadiene structure in the polybutadiene is preferably 70% by mass or more, and more preferably 90% by mass or more.
Further, in the 1,2-polybutadiene structure, 50% by mass or more is preferably a syndiotactic structure in order to improve crystallinity.
The content ratio of the 1,2-polybutadiene structure in the polybutadiene is preferably 70% by mass or more from the viewpoint of reactivity with the radical polymerization initiator described later, and in the 1,2-polybutadiene structure, 90% by mass. The above is more preferably a syndiotactic structure.
The 1,2-polybutadiene structure has high mobility at the unsaturated bond site, thereby increasing reactivity with a radical polymerization initiator described later, and improving hot offset resistance.
The mass% of the polybutadiene structure and the mass% of the structure formed by 1,2-polybutadiene can be measured using a general analytical technique, and for example, a technique such as nuclear magnetic resonance (NMR) can be applied. .

The melting point of the aliphatic hydrocarbon resin having an unsaturated bond (for example, polybutadiene) is preferably 60 ° C. or higher and 80 ° C. or lower, and more preferably 65 ° C. or higher and 75 ° C. or lower.
When the melting point is 60 ° C. or higher, the storage stability at a high temperature is further improved, and when the melting point is 80 ° C. or lower, the glossiness is further improved.
In the present invention, the melting point of a polymer or the like 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.
The peak temperature of the maximum endothermic peak in the obtained DSC curve is defined as the melting point.

In the present invention, the aliphatic hydrocarbon resin having an unsaturated bond is crosslinked.
Examples of the crosslinking method include using any crosslinking agent that reacts with the unsaturated bond site. As the crosslinking agent, a radical polymerization initiator is preferable from the viewpoint of improving hot offset resistance.
The crosslinked product obtained by crosslinking an aliphatic hydrocarbon resin having an unsaturated bond is preferably dispersed in the form of fine particles having a volume-based average particle diameter of 10 nm or more and 1000 nm or less in the toner particles.
When the volume-based average particle diameter is 10 nm or more, the glossiness as an image is further improved, and when it is 1000 nm or less, the hot offset resistance is further improved.
In order to disperse the crosslinked product in a fine particle form in the toner, it is preferable to produce a particulate crosslinked product having a volume-based average particle diameter of 10 nm or more and 1000 nm or less, and the emulsion aggregation method described later.
The particle diameter is measured by using a cryomicrotome, preparing an ultra-thin section of toner with a film thickness of about 60 nm, staining the ultra-thin section with ruthenium, and observing with a transmission electron microscope. Can be measured.

The content of the crosslinked product of the aliphatic hydrocarbon resin having an unsaturated bond is preferably 1.0% by mass or more and 8.0% by mass or less based on the total mass of the resin component. More preferably, the content is not less than mass% and not more than 3.0 mass%.
When the content of the crosslinked product is 1.0% by mass or more, the effect of hot offset resistance is enhanced, and when the content is 8.0% by mass or less, the low-temperature fixability and glossiness are further improved.

The resin component may further contain an acid group-containing olefin copolymer, for example, a modified polyethylene resin having a carboxy group.
The modified polyethylene resin having a carboxy group is a resin in which other components are randomly copolymerized, block copolymerized or graft copolymerized with a polyolefin resin mainly composed of polyethylene, and these resins are modified by a polymer reaction. Point to what you let.
Examples of the component to be copolymerized include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid and the like.
Specifically, an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer and the like can be suitably exemplified.
The carboxy group present in the modified polyethylene resin forms a hydrogen bond with the hydroxyl group on the paper surface, the adhesion between the toner and the paper is increased, and the fixed product is not erased by an eraser or the like.
In addition, the modified polyethylene resin having a carboxy group has a higher melting point than that of the ester group-containing olefin copolymer, and by containing it, the storage stability at high temperature is improved.
The content of the modified polyethylene resin having a carboxy group is preferably 10% by mass or more and less than 50% by mass, and more preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the resin component.
When the content is in the above range, the adhesiveness to paper can be improved while suppressing the environmental fluctuation of charging property.
The acid value of the modified polyethylene resin having a carboxy group is preferably 50 mgKOH / g or more and 300 mgKOH / g or less, and 80 mgKOH / g or more and 200 mgKOH / g or less from the viewpoint of sufficient adhesion to paper and chargeability improvement. More preferably.

The acid value is the number of mg of potassium hydroxide required to neutralize an acid component such as free fatty acid or resin acid contained in 1 g of a sample. The acid value is measured according to JIS K 0070-1992. Specifically, the acid value is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95% by volume) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 mL of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

The softening point of the modified polyethylene resin having a carboxy group is 100 ° C. or more and 140 ° C. or less from the viewpoint of blocking resistance, adhesion between the toner and paper and compatibility with the ester group-containing olefin copolymer. Is preferred.
The melting point of the modified polyethylene resin having a carboxy group is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower, from the viewpoints of low-temperature fixability and storage stability.

The resin component contains an ester group-containing olefin copolymer, a cross-linked aliphatic hydrocarbon resin having an unsaturated bond, and other heavy resins other than a modified polyethylene resin having a carboxy group to such an extent that the effects of the present invention are not impaired. A combination may be used in combination.
Specifically, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Styrene copolymers such as copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers; polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylics Examples include resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyethylene resins, polypropylene resins, and the like.

The toner particles may contain an aliphatic hydrocarbon having a melting point of 50 ° C. or higher and 100 ° C. or lower.
The content of the aliphatic hydrocarbon is preferably 1 part by mass or more and 40 parts by mass or less, and preferably 10 parts by mass or more and 35 parts by mass with respect to 100 parts by mass of the resin component, from the viewpoint of low temperature fixability and chargeability. The content is more preferably 10 parts by mass or more and 30 parts by mass or less.
When the aliphatic hydrocarbon is heated, plasticization of the ester group-containing olefin copolymer can be promoted. Therefore, by containing an aliphatic hydrocarbon in the toner particles, the ester group-containing olefin copolymer forming a matrix in the toner particles can be plasticized to further improve the low-temperature fixability.
Furthermore, the aliphatic hydrocarbon having a melting point of 50 ° C. or more and 100 ° C. or less can also act as a crystal nucleating agent for the ester group-containing olefin copolymer. Therefore, the micro mobility of the ester group-containing olefin copolymer is suppressed, and the chargeability is further improved.
Specific examples of the aliphatic hydrocarbon include aliphatic hydrocarbons having 20 to 60 carbon atoms, such as hexacosane, triacontane, and hexatriacontane.

The toner particles may contain silicone oil as a release agent.
Release agents generally used for toners such as alkyl waxes tend to compatibilize ester group-containing olefin copolymers, and a release effect is difficult to obtain.
In addition, when the toner particles contain a colorant, by adding silicone oil, the dispersibility of the colorant is improved and an image with a high density is easily obtained.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, carboxy-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 1000 mm ² / s or less, and more preferably less 20 mm ² / s or more 1000 mm ² / s.
The silicone oil content is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component from the viewpoint of obtaining good separability while suppressing a decrease in fluidity. The amount is more preferably no less than 25 parts by mass and even more preferably no less than 5 parts by mass and no greater than 20 parts by mass.

The toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black, a magnetic material, or a color adjusted to black using a yellow colorant, a magenta colorant, and a cyan colorant.
In these colorants, 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 the form of a solid solution.
The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in the toner.
The content of the colorant 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 component.

The toner preferably has a volume-based median diameter of 3.0 μm or more and 10.0 μm or less, more preferably 4.0 μm or more and 7.0 μm or less from the viewpoint of obtaining a high-definition image.
The volume-based median diameter of the toner may be measured by using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter Co.) by the Coulter method.

The method for producing the toner of the present invention includes:
A method for producing a toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
A preparation step of preparing a resin fine particle dispersion in which the resin fine particles for producing the resin component are dispersed in an aqueous medium; and
A crosslinking step of crosslinking the aliphatic hydrocarbon resin having an unsaturated bond present in the resin fine particles using a crosslinking agent;
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the above formula (1);
Having at least one monomer unit Y2 selected from the group consisting of the monomer unit represented by the above formula (2) and the monomer unit represented by the above formula (3),
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
Content of this monomer unit Y2 is 3 to 35 mass% with respect to the total mass of this ester group containing olefin type copolymer, It is characterized by the above-mentioned.

A method for producing a toner having the toner particles includes a preparation step of preparing a resin fine particle dispersion in which resin fine particles for generating a resin component are dispersed in an aqueous medium, and an unsaturated bond present in the resin fine particles. A crosslinking step of crosslinking the aliphatic hydrocarbon resin with a crosslinking agent is included.
Resin fine particles in which a crosslinked product is finely dispersed can be prepared by crosslinking an aliphatic hydrocarbon resin having an unsaturated bond in the state of a resin fine particle dispersion dispersed in an aqueous medium. As a result, the low-temperature fixability is good and the hot offset resistance can be improved.
Among the methods for producing toner particles in an aqueous medium, it is preferable to use an 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.
That is, it contains an aliphatic hydrocarbon resin having an unsaturated bond, forms fine particles sufficiently smaller than the toner particles, and is further finely dispersed in the toner particles by crosslinking with a crosslinking agent during the production process. A crosslinked product can be formed. As a result, the low-temperature fixability and hot offset resistance are further improved.

In the emulsion aggregation method, after the preparation step of preparing the resin fine particle dispersion,
An aggregation step of aggregating the resin fine particles to form aggregate particles, and
It is preferable to further have a fusing step of fusing the aggregate particles by heating.
The crosslinking step is a step of crosslinking an aliphatic hydrocarbon resin having an unsaturated bond existing in the resin fine particles by using a crosslinking agent between the preparation step of preparing the resin fine particle dispersion and the aggregation step. It is preferable that
Furthermore, in addition to the above steps, a cooling step, a washing step, a drying step, and the like may be performed.

Hereinafter, the toner production method using the emulsion aggregation method will be specifically described, but the present invention is not limited thereto.
<Preparation process for preparing resin fine particle dispersion>
Although the resin fine particle dispersion can be prepared by a known method, the following methods can be preferably exemplified.
For example, a resin fine particle A dispersion in which resin fine particles A containing an ester group-containing olefin copolymer and not containing an aliphatic hydrocarbon resin having an unsaturated bond are dispersed in an aqueous medium, and a fat having an unsaturated bond Two resin fine particle B dispersions in which resin fine particles B containing a group hydrocarbon resin are dispersed in an aqueous medium are prepared.
By using the two resin fine particle dispersions, it is possible to control the dispersion state in the toner particles of the crosslinked aliphatic hydrocarbon resin having an unsaturated bond as described later, and the hot offset resistance and glossiness are remarkable. Can be improved.
For example, the resin fine particle A dispersion is prepared as follows.
Only the ester group-containing olefin copolymer is 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, the organic solvent is removed to prepare a resin fine particle A dispersion in which resin fine particles A are dispersed.
On the other hand, the resin fine particle B dispersion is prepared as follows, for example.
An aliphatic hydrocarbon resin having at least an unsaturated bond is 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, the organic solvent is removed to prepare a resin fine particle B dispersion in which the resin fine particles B are dispersed.

The resin fine particle B dispersion may be a dispersion in which resin fine particles B containing an ester group-containing olefin copolymer and an aliphatic hydrocarbon resin having an unsaturated bond are dispersed in an aqueous medium.
In this case, the resin group B may be formed by co-emulsification by dissolving both the ester group-containing olefin copolymer and the aliphatic hydrocarbon resin having an unsaturated bond.
When the co-emulsification method is used, the ester group-containing olefin copolymer and the unsaturated hydrocarbon aliphatic hydrocarbon resin are uniformly mixed in the fine particles in the atomized organic phase, and both in the toner particles. The compatibility is further improved, and the hot offset resistance is further improved.
More specifically, an ester group-containing olefin copolymer and an aliphatic hydrocarbon resin having an unsaturated bond are dissolved by heating in an organic solvent, and a surfactant or a basic compound is added. Subsequently, a co-emulsion (resin fine particle B dispersion) containing a resin is prepared by slowly adding an aqueous medium while applying a shearing force with a homogenizer or the like.
Alternatively, a co-emulsion liquid containing a resin is prepared by applying a shearing force with a homogenizer or the like after the addition of the aqueous medium. Thereafter, the organic solvent is removed by heating or decompression to prepare a resin fine particle B dispersion.
The content of the aliphatic hydrocarbon resin having an unsaturated bond in the resin fine particle B is preferably 5% by mass or more and 20% by mass or less with respect to the total amount of the resin constituting the resin fine particle B. By setting the content to 5% by mass or more, the reactivity of the aliphatic hydrocarbon resin having an unsaturated bond in the resin fine particles is increased, and the crosslinking process proceeds smoothly. On the other hand, when the amount is 20% by mass or less, excessive reaction in the crosslinking step can be prevented, and the hot offset resistance of the toner is further improved.

When the modified polyethylene resin having a carboxy group is contained in resin fine particles, it may be dissolved in an organic solvent together with an ester group-containing olefin copolymer and / or an aliphatic hydrocarbon resin having an unsaturated bond.
When the resin fine particles contain the modified polyethylene resin having a carboxy group, the reactivity of the fine particles in the emulsion aggregation method is increased, and the particle size distribution of the obtained toner particles is improved.
In preparing the resin fine particle dispersion, the amount of the resin component dissolved in the organic solvent is preferably 10 parts by mass or more and 50 parts by mass or less, and 30 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the organic solvent. It is more preferable to set it as a part or less.
Any organic solvent can be used as long as it can dissolve the resin, but a solvent having high solubility in an ester group-containing olefin copolymer such as toluene, xylene, and ethyl acetate is preferable.
The surfactant is not particularly limited. For example, sulfate ester salt type, sulfonate type, carboxylate type, phosphate ester type, soap type 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 basic compound include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.

The volume-based median diameter of the resin fine particles is preferably 50 nm or more and 1000 nm or less, and more preferably 100 nm or more and 600 nm or less. When the median diameter is within the above range, toner particles having a desired particle diameter are easily obtained.
In particular, the volume-based median diameter of the resin fine particles B is preferably 50 nm or more and 1000 nm or less, and more preferably 100 nm or more and 600 nm or less. By setting the median diameter in the above range, the dispersion diameter of the crosslinked fine particles in the toner particles becomes 50 nm or more and 1000 nm or less, which is preferable from the viewpoint of achieving both hot offset resistance and glossiness.
The volume-based median diameter is measured using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150, manufactured by Nikkiso).

<Crosslinking process>
The crosslinking step is a step of crosslinking an aliphatic hydrocarbon resin having an unsaturated bond present in the resin fine particles using a crosslinking agent.
The cross-linking step is a step of cross-linking an aliphatic hydrocarbon resin having an unsaturated bond existing in the resin fine particles using a cross-linking agent between the preparation step of preparing the resin fine particle dispersion and the aggregation step described later. It is preferable that
Furthermore, it is preferable to provide a crosslinking step between the end of the preparation step for preparing the resin fine particle dispersion and the start of the aggregation step.
By carrying out the crosslinking step at the above time, sufficiently fine crosslinked fine particles having a uniform particle diameter can be formed, and the low-temperature fixability and hot offset resistance are further improved.
More specifically, the crosslinking reaction may be advanced by adding a crosslinking agent and heating the resin fine particle B dispersion containing an aliphatic hydrocarbon resin having an unsaturated bond while stirring.

The crosslinking agent is preferably a radical polymerization initiator.
The radical polymerization initiator includes oil-soluble and water-soluble initiators, and any initiator may be used, but a water-soluble radical polymerization initiator is preferable from the viewpoint of uniformity of reaction.
Examples of the radical polymerization initiator include the following compounds.
2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-amidino) Propane) nitriles such as propane) hydrochloride; diacyl peroxides such as acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide; Di-t-butyl peroxide, t-butyl-α-cumyl peroxide, dicumyl Dialkyl peroxides such as oxides; t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxylaurate, t- Peroxyesters such as butyl peroxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate; t-butylhydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide Hydroperoxide such as cumene hydroperoxide and di-isopropylbenzene hydroperoxide; peroxycarbonate such as t-butylperoxyisopropyl carbonate; inorganic peroxides such as hydrogen peroxide; potassium persulfate and sodium persulfate And persulfates such as thorium and ammonium persulfate.
It is preferable that the addition amount of a crosslinking agent (especially radical polymerization initiator) is 0.1 to 20 parts by mass with respect to 100 parts by mass of an aliphatic hydrocarbon resin having an unsaturated bond.
When the addition amount of the crosslinking agent is within the above range, the crosslinking reaction is sufficiently performed.
The crosslinking agent may be added as a solid, or may be added after being dissolved in water.
The heating temperature is preferably, for example, 10 to 40 ° C. higher than the 10-hour half-life temperature of the radical polymerization initiator. Moreover, it is preferable that heating time is 1 hour or more and 12 hours or less. When the heating temperature and the heating time are within the above ranges, the crosslinking reaction can sufficiently proceed and a crosslinked structure can be obtained. From the viewpoint of hot offset resistance, a crosslinked product obtained by crosslinking an aliphatic hydrocarbon resin having an unsaturated bond is crosslinked to such an extent that it does not dissolve in heated toluene (for example, toluene heated to about 90 ° C.). preferable.

<Aggregation process>
In the aggregation step, for example, the resin fine particle A dispersion and the resin fine particle B dispersion are mixed with a colorant fine particle dispersion, an aliphatic hydrocarbon fine particle dispersion, and a silicone oil emulsion to prepare a mixture, In this step, the fine particles contained in the prepared mixed liquid are aggregated to form aggregate particles. As a method for forming the aggregate particles, a method of adding and mixing an aggregating agent into the above mixed solution, raising the temperature, and appropriately applying mechanical power or the like can be suitably exemplified.
The colorant fine particle dispersion is prepared by dispersing the colorant. The colorant fine particles are dispersed by a known method. For example, a media-type disperser such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure counter-collision disperser is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.
The aliphatic hydrocarbon fine particle dispersion and the silicone oil emulsion are prepared by dispersing each material in an aqueous medium. Each material is 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 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 flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum; polyaluminum chloride And multivalent metal salts. From the viewpoint of particle diameter controllability in the aggregation process, a metal salt of a divalent metal such as calcium chloride or magnesium sulfate is preferable.
The addition and mixing of the flocculant is preferably performed in a temperature range from room temperature to 75 ° C. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The said mixing can be performed using a well-known mixing apparatus, a homogenizer, a mixer, etc.
The volume-based median diameter of the aggregate particles formed in the aggregation process is not particularly limited, but is usually about 4.0 μm or more and 7.0 μm or less so as to be the same as the median diameter of the toner particles to be obtained. It is good to control. This control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition and mixing of the flocculant and the like and the conditions of the stirring and mixing.
The volume-based median diameter of the aggregate particles is measured using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter Co.) by the Coulter method.

<Fusion process>
The fusing step is a step of producing particles in which the surface of the agglomerate particles is smoothed by heating and fusing the agglomerate particles above the melting point of the ester group-containing olefin copolymer.
Before entering the primary fusion step, a chelating agent, a pH adjusting agent, a surfactant and the like can be appropriately added in order to prevent fusion between the obtained resin particles.
Examples of chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium and sodium citrate, nitrilotriacetate (NTA) salts, both 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 ester group-containing olefin copolymer contained in the aggregate particles to the ester group-containing olefin copolymer or a modified polyethylene resin having a carboxy group (hereinafter referred to as acid group-containing olefin copolymer). It may be between the temperatures at which the polymer) is also thermally decomposed. As for the heat 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 time of heat fusion depends on the temperature of heating and cannot be defined unconditionally, but is generally about 10 minutes to 10 hours.

<Cooling process>
The cooling step is a step of cooling the temperature of the aqueous dispersion containing the resin particles obtained in the fusion step to a temperature lower than the crystallization temperature of the ester group-containing olefin copolymer.
By performing the cooling to a temperature lower than the crystallization temperature, generation of coarse particles can be prevented. Moreover, a cooling rate is about 0.1-50 degreeC / min.
Further, it is preferable to carry out annealing for promoting the crystallization by maintaining the ester group-containing olefin copolymer at a temperature at which the crystallization rate is high during or after cooling. By maintaining the temperature at 30 to 70 ° C., crystallization is promoted, and as a result, the blocking resistance of the toner is further improved.

<Washing process>
Impurities in the resin particles can be removed by repeatedly washing and filtering the resin particles produced through the above steps.
Specifically, it is preferable that the resin particles are washed with an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, and further washed with pure water.
Washing with pure water can remove metal salts, surfactants, and the like in the resin particles by repeating filtration several 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 washed resin particles may be dried to obtain toner particles.
The toner particles may be used as it is. If necessary, add inorganic fine particles such as silica, alumina, titania, calcium carbonate, and resin fine particles such as vinyl resin, polyester resin, and silicone resin by applying a shearing force in a dry state to add toner. It is good. The inorganic fine particles and resin fine particles function as external additives such as fluidity aids and cleaning aids.

  Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, the aspect of this 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 example of resin fine particle A1 dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries) 300 parts-Ethylene-vinyl acetate copolymer [EVA-A] 100 parts (R ¹ = H, R ² = H, R ³ = CH _3, content of monomer unit Y2: 15 Mass%, acid value: 0 mg KOH / g, weight average molecular weight (Mw): 110000, softening point (Tm): 128 ° C., melting point: 86 ° C., elongation at break: 700%, (l + m + n) /W=1.00)
25 parts of acid group-containing olefin copolymer A [EMA-A] (ethylene-methacrylic acid copolymer, softening point (Tm): 123 ° C., melting point: 90 ° C., acid value: 90 mgKOH / g)
The above formulations were mixed and dissolved at 90 ° C.
Separately, 0.7 parts of sodium dodecylbenzenesulfonate, 1.5 parts of sodium laurate and 1.65 parts of N, N-dimethylaminoethanol were added to 700 parts of ion-exchanged water and dissolved by heating at 90 ° C.
Next, the above toluene solution and aqueous solution were mixed together, 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 A1 dispersion) having a resin fine particle A1 concentration of 20%.
The volume-based median diameter of the resin fine particles A1 was measured using a dynamic light scattering particle size distribution meter (Nanotrack: manufactured by Nikkiso), and was 0.40 μm.

<Production example of resin fine particle A2 dispersion>
[EVA-A] 100 parts, [EVA-A] 50 parts, and ethylene-vinyl acetate copolymer [EVA-B] (R ¹ = H, R ² = H, R ³ = CH _3, monomer unit Content of Y2: 15% by mass, acid value: 0 mg KOH / g, softening point (Tm): 83 ° C., melting point: 77 ° C., (l + m + n) /W=1.00) Resin fine particles A1 except for changing to 50 parts Resin fine particle A2 dispersion was obtained in the same manner as in the preparation of the dispersion. The volume-based median diameter of the obtained resin fine particles A2 was 0.33 μm. The elongation at break in a state where [EVA-A] and [EVA-B] were mixed in an equal amount was 450%.

<Example of production of resin fine particle A3 dispersion>
The resin fine particle A3 dispersion was prepared in the same manner as in the production example of the resin fine particle A2 dispersion except that the acid group-containing olefin copolymer A [EMA-A] and N, N-dimethylaminoethanol were not used. Obtained. The volume-based median diameter of the obtained resin fine particles A3 was 1.23 μm.

<Production example of resin fine particle A4 dispersion>
[EVA-A] is an ethylene-ethyl acrylate copolymer [EEA-A] (R ¹ = H, R ⁴ = H, R ⁵ = C ₂ H _5, content of monomer unit Y2: 15% by mass, Production of resin fine particle A1 dispersion except that the acid value was changed to 0 mgKOH / g, softening point (Tm): 125 ° C., melting point: 87 ° C., elongation at break: 800%, (l + m + n) /W=1.00) In the same manner as in the example, a resin fine particle A4 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A4 was 0.54 μm.

<Production example of resin fine particle A5 dispersion>
[EVA-A] 100 parts, [EVA-A] 80 parts, and polyester resin A [PES-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 , Softening point (Tm): 120 ° C., glass transition temperature (Tg): 70 ° C., acid value: 13 mg KOH / g] Except for changing to 20 parts, resin fine particle A5 A dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A5 was 0.33 μm.

<Production example of resin fine particle A6 dispersion>
[EVA-A] is changed to ethylene-vinyl acetate-vinyl valerate copolymer [EVA-C] (R ¹ = H, R ² = H, R ³ = CH _3, monomer unit Y2 content: 15% by mass) Content of monomer unit derived from vinyl valerate [Formula (4)]: 4% by mass, acid value: 0 mg KOH / g, weight average molecular weight (Mw): 120,000, softening point (Tm): 130 ° C., melting point: A resin fine particle A6 dispersion was obtained in the same manner as in the production example of the resin fine particle A1 dispersion except that the temperature was changed to 75 ° C., elongation at break: 600%, (l + m + n) /W=0.96). The volume-based median diameter of the obtained resin fine particles A6 was 0.44 μm.

<Production Example of Resin Fine Particle A7 Dispersion>
[EVA-A], ethylene-vinyl acetate-vinyl valerate copolymer [EVA-D] (R ¹ = H, R ² = H, R ³ = CH _3, monomer unit Y2 content: 5% by mass Content of monomer unit derived from vinyl valerate [formula (4)]: 25% by mass, acid value: 0 mgKOH / g, weight average molecular weight (Mw): 110000, softening point (Tm): 118 ° C., melting point: A resin fine particle A7 dispersion was obtained in the same manner as in the production example of the resin fine particle A1 dispersion, except that the temperature was changed to 71 ° C., elongation at break: 550%, (l + m + n) /W=0.75). The volume-based median diameter of the obtained resin fine particles A7 was 0.42 μm.

<Production Example of Resin Fine Particle A8 Dispersion>
[EVA-A] is an ethylene-vinyl acetate copolymer [EVA-E] (R ¹ = H, R ² = H, R ³ = CH _3, monomer unit Y2 content: 2% by mass, acid value: 0 mg KOH / g, melting point: 105 ° C., softening point (Tm): 156 ° C., elongation at break: 600%, (l + m + n) /W=1.00) Thus, a resin fine particle A8 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A8 was 0.51 μm.

<Production example of resin fine particle A9 dispersion>
[EVA-A] is an ethylene-vinyl acetate copolymer [EVA-F] (R ¹ = H, R ² = H, R ³ = CH _3, monomer unit Y2 content: 41% by mass, acid value: 0 mg KOH / g, softening point (Tm): 160 ° C., melting point: 40 ° C., elongation at break: 870%, (l + m + n) /W=1.00) Thus, a resin fine particle A9 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A9 was 0.51 μm.

<Production Example of Resin Fine Particle A10 Dispersion>
Without using [EVA-A] and [EMA-A], polyester resin A [PES-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, Softening point (Tm): 120 ° C., glass transition temperature (Tg): 70 ° C., acid value: 13 mg KOH / g], except that the amount used was 125 parts, as in the production example of resin fine particle A1 dispersion, A resin fine particle A10 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A10 was 0.25 μm.

<Production Example of Resin Fine Particle A11 Dispersion>
[PES-A], crystalline polyester resin A [CPES-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 A11 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A11 was 0.25 μm.

<Example of production of crosslinked resin fine particle B1 dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries) 300 parts-Ethylene-vinyl acetate copolymer [EVA-A] 90 parts-Aliphatic hydrocarbon resin [Al-A] having an unsaturated bond [polybutadiene (1,2- Content ratio of polybutadiene structure: 90% by mass, ratio of syndiotactic structure: 50% by mass, melting point: 70 ° C., weight average molecular weight (Mw): 205000)]
-Acid group containing olefin copolymer A [EMA-A] 25 parts The above formulation was mixed and dissolved at 90 ° C.
Separately, 0.7 parts of sodium dodecylbenzenesulfonate, 1.5 parts of sodium laurate, and 1.6 parts of N, N-dimethylaminoethanol were added to 700 parts of ion-exchanged water and dissolved by heating at 90 ° C.
Next, the above toluene solution and aqueous solution were mixed together, 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 B1 dispersion) having a resin fine particle B1 concentration of 20%.
The volume-based median diameter of the resin fine particles B1 was measured by using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.40 μm.
Subsequently, 0.5 part of sodium persulfate was added as a radical polymerization initiator while stirring 500 parts of the dispersion of resin fine particles B1.
Then, it heated to 90 degreeC and stirred for 3 hours. Furthermore, the crosslinked resin fine particle B1 dispersion liquid was obtained by cooling to room temperature. The volume-based median diameter of the obtained crosslinked resin fine particles B1 was 0.40 μm.

<Production Example of Crosslinked Resin Fine Particle B2 Dispersion>
Resin fine particle B2 dispersion liquid as in the production example of the crosslinked resin fine particle B1 dispersion liquid except that 90 parts of [EVA-A] are changed to 45 parts of [EVA-A] and 45 parts of [EVA-B] And the crosslinked resin fine particle B2 dispersion liquid was obtained. The volume-based median diameter of the obtained resin fine particles B2 and crosslinked resin fine particles B2 was 0.33 μm.

<Example of production of crosslinked resin fine particle B3 dispersion>
[Al-A], aliphatic hydrocarbon resin having an unsaturated bond [Al-B] [polybutadiene (content of 1,2-polybutadiene structure: 92% by mass, ratio of syndiotactic structure: 55% by mass) , Melting point: 95 ° C., weight average molecular weight (Mw): 210000)], in the same manner as in the production example of the crosslinked resin fine particle B2 dispersion, resin fine particle B3 dispersion and crosslinked resin fine particle B3 dispersion were obtained. . The volume-based median diameter of the obtained resin fine particles B3 and crosslinked resin fine particles B3 was 0.42 μm.

<Example of production of crosslinked resin fine particle B4 dispersion>
[Al-A], aliphatic hydrocarbon resin having an unsaturated bond [Al-C] [polybutadiene (content of 1,2-polybutadiene structure: 90% by mass, ratio of syndiotactic structure: 20% by mass) , Melting point: none, weight average molecular weight (Mw): 3000)] In the same manner as in the production example of the crosslinked resin fine particle B2 dispersion, resin fine particle B4 dispersion and crosslinked resin fine particle B4 dispersion were obtained. The volume-based median diameter of the obtained resin fine particles B4 and crosslinked resin fine particles B4 was 0.46 μm.

<Example of production of crosslinked resin fine particle B5 dispersion>
[Al-A] is an aliphatic hydrocarbon resin having an unsaturated bond [Al-D] [1,4-poly (1-propylbuta-1,3-diene) (melting point: 40 ° C., weight average molecular weight ( Mw): 120,000)] In the same manner as in the production example of the crosslinked resin fine particle B2 dispersion, resin fine particle B5 dispersion and crosslinked resin fine particle B5 dispersion were obtained. The volume-based median diameter of the obtained resin fine particles B5 and crosslinked resin fine particles B5 was 0.55 μm.

<Example of production of crosslinked resin fine particle B6 dispersion>
Crosslinking except that acid group-containing olefin copolymer A [EMA-A] and N, N-dimethylaminoethanol were not used and the amount of aliphatic hydrocarbon resin [Al-A] was 7.8 parts. In the same manner as in the production example of the resin fine particle B2 dispersion, a resin fine particle B6 dispersion and a crosslinked resin fine particle B6 dispersion were obtained. The volume-based median diameter of the obtained resin fine particles B6 and crosslinked resin fine particles B6 was 1.3 μm.

<Example of production of crosslinked resin fine particle B7 dispersion>
Resin fine particle B7 dispersion and crosslinked resin fine particle B7 dispersion were the same as in the production example of the crosslinked resin fine particle B1 dispersion except that [EVA-A] was changed to ethylene-ethyl acrylate copolymer [EEA-A]. A liquid was obtained. The volume-based median diameter of the obtained resin fine particles B7 and crosslinked resin fine particles B7 was 0.52 μm.

<Example of production of crosslinked resin fine particle B8 dispersion>
[EVA-A] As in the production example of the crosslinked resin fine particle B1 dispersion, except that 90 parts were changed to [EVA-A] 67.5 parts and polyester resin A [PES-A] 22.5 parts. Thus, a resin fine particle B8 dispersion and a crosslinked resin fine particle B8 dispersion were obtained. The volume-based median diameter of the obtained resin fine particles B8 and crosslinked resin fine particles B8 was 0.52 μm.

<Example of production of crosslinked resin fine particle B9 dispersion>
Resin fine particle B9 dispersion and cross-linked resin were produced in the same manner as in the production example of cross-linked resin fine particle B1 dispersion except that [EVA-A] was changed to ethylene-vinyl acetate-vinyl valerate copolymer [EVA-C]. A fine particle B9 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles B9 and crosslinked resin fine particles B9 was 0.44 μm.

<Example of production of crosslinked resin fine particle B10 dispersion>
Resin fine particle B10 dispersion and crosslinked resin in the same manner as in the production example of the crosslinked resin fine particle B1 dispersion except that [EVA-A] was changed to ethylene-vinyl acetate-vinyl valerate copolymer [EVA-D]. A fine particle B10 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles B10 and crosslinked resin fine particles B10 was 0.38 μm.

<Production Example of Crosslinked Resin Fine Particle B11 Dispersion>
Cross-linked resin except that the amount of [EVA-A] used was changed to 43.75 parts, the amount of [Al-A] used was changed to 2.5 parts, and [EVA-B] was added to 43.75 parts. In the same manner as in the production example of the fine particle B1 dispersion, resin fine particle B11 dispersion and crosslinked resin fine particle B11 dispersion were obtained. The volume-based median diameter of the obtained resin fine particles and crosslinked resin fine particles was 0.42 μm.

<Example of producing crosslinked resin fine particle B12 dispersion>
Resin fine particle B12 dispersion and crosslinked resin fine particle B12 were produced in the same manner as in the production example of the crosslinked resin fine particle B1 dispersion except that the use of [EVA-A] was stopped and the amount of [Al-A] was changed to 100 parts. A dispersion was obtained. The volume-based median diameter of the obtained resin fine particles B12 and crosslinked resin fine particles B12 was 0.51 μm.

<Example of production of crosslinked resin fine particle B13 dispersion>
[Al-A] is converted into polyester resin B [composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane: phthalic acid: terephthalic acid = 15: 35: 35: 15], number average molecular weight (Mn): 3,000, weight average molecular weight (Mw): 12,000, softening point (Tm): 96 ° C., glass transition temperature (Tg): 52 ° C., acid value: 10 mgKOH / g] The resin fine particle B13 dispersion and the cross-linked product were obtained in the same manner as in the production example of the crosslinked resin fine particle B6 dispersion. A resin fine particle B13 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles B13 and crosslinked resin fine particles B13 was 0.15 μm.

<Example of production of crosslinked resin fine particle B14 dispersion>
Resin fine particle B14 dispersion and crosslinked resin fine particle B14 dispersion were obtained in the same manner as in the production example of the crosslinked resin fine particle B1 dispersion except that [EVA-A] was changed to [EVA-E]. The volume-based median diameter of the obtained resin fine particles B14 and crosslinked resin fine particles B14 was 0.15 μm.

<Example of production of crosslinked resin fine particle B15 dispersion>
Resin fine particle B15 dispersion and crosslinked resin fine particle B15 dispersion were obtained in the same manner as in the production example of the crosslinked resin fine particle B1 dispersion except that [EVA-A] was changed to [EVA-F]. The volume-based median diameter of the obtained resin fine particles B15 and crosslinked resin fine particles B15 was 0.56 μm.

<Example of production of crosslinked resin fine particle B16 dispersion>
Resin fine particle B16 dispersion liquid as in the production example of the crosslinked resin fine particle B1 dispersion liquid except that 115 parts of polyester resin A [PES-A] was used without using [EVA-A] and [EMA-A]. And the crosslinked resin fine particle B16 dispersion liquid was obtained. The volume-based median diameter of the obtained resin fine particles B16 and crosslinked resin fine particles B16 was 0.33 μm.

<Production Example of Colorant Fine Particle Dispersion>
Colorant 10.0 parts (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.5 parts ・ Ion-exchanged water 88.5 parts Mix and dissolve above, and use high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) Then, an aqueous dispersion (colorant fine particle dispersion) having a concentration of 10% of the colorant fine particles obtained by dispersing the colorant was prepared for about 1 hour. 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.

<Production example of aliphatic hydrocarbon fine particle dispersion>
Aliphatic hydrocarbon 20.0 parts (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa)
・ 1.0 part of anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK)
-79.0 parts of ion-exchanged water was charged into a mixing vessel equipped with a stirrer, and then heated to 90 ° C and circulated to Claremix W Motion (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 dispersion is cooled to 40 ° C. under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 ° C./min. A liquid (aliphatic hydrocarbon fine particle dispersion) was obtained. The volume-based median diameter of the aliphatic hydrocarbon fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

<Example of production of silicone oil emulsion>
・ Silicone oil 20.0 parts (Dimethyl silicone oil, Shin-Etsu Chemical: KF96-50CS)
・ 1.0 parts of anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) ・ 79.0 parts of ion-exchanged water are mixed and dissolved, and using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) An aqueous dispersion (silicone oil emulsion) 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.

<Production Example of Toner 1>
-Resin fine particle A1 dispersion 375 parts-Crosslinked resin fine particle B1 dispersion 125 parts-Colorant fine particle dispersion 80 parts-Aliphatic hydrocarbon fine particle dispersion 150 parts-Silicone oil emulsion 100 parts-Ion exchange water 110 parts Each material was put into a round stainless steel flask and mixed, and then 60 parts 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 rotation speed so that the mixed solution was stirred.
After holding at 73 ° C. for 20 minutes, it was confirmed that the volume-based median diameter of the formed aggregate particles was about 6.0 μm.
After adding 340 parts of 5% ethylenediamine tetraacetate aqueous solution to the dispersion containing the aggregate particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the aggregate particles were fused by maintaining at 98 ° C. 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 ° C. and filtration and solid-liquid separation, the filtrate was washed with 0.5% aqueous ethylenediaminetetraacetate solution and further washed with ion-exchanged water.
After the washing, the toner particles 1 having a volume-based median diameter of 5.4 μm were obtained by drying using a vacuum dryer.
100 parts of the toner particles 1 were subjected to a hydrophobic treatment of 1.5 parts of silica fine particles having a primary particle number average particle size of 10 nm and a hydrophobic treatment having a primary particle number average particle size of 100 nm. Toner 1 was obtained by dry mixing 2.5 parts of silica fine particles with a Henschel mixer (Mitsui Mine). The structural conditions of the obtained toner 1 are shown in Table 1, Table 2, and Table 3.

<Production Example of Toner 2>
A toner 2 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A2 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B2 dispersion. The volume-based median diameter of the obtained toner 2 was 5.3 μm.

<Production Example of Toner 3>
Toner 3 was obtained in the same manner as in Toner 2 except that the amount of resin fine particle A2 dispersion used was 125 parts and the amount of crosslinked resin fine particle B2 dispersion used was 375 parts. The obtained toner 3 had a volume-based median diameter of 5.5 μm.

<Production Example of Toner 4>
Toner 4 was obtained in the same manner as in the production example of toner 2 except that the use of the resin fine particle A2 dispersion was stopped and the amount of the crosslinked resin fine particle B2 dispersion used was 500 parts. The obtained toner 4 had a volume-based median diameter of 5.8 μm.

<Production Example of Toner 5>
Toner 5 was obtained in the same manner as in Toner 2 except that the amount of resin fine particle A2 dispersion used was 475 parts and the amount of crosslinked resin fine particle B2 dispersion used was 25 parts. The obtained toner 5 had a volume-based median diameter of 5.5 μm.

<Production Example of Toner 6>
A toner 6 was obtained in the same manner as in the production example of the toner 2 except that the use of the aliphatic hydrocarbon fine particle dispersion was stopped. The obtained toner 6 had a volume-based median diameter of 5.2 μm.

<Production Example of Toner 7>
A toner 7 was obtained in the same manner as in the production example of the toner 2 except that the use of the aliphatic hydrocarbon fine particle dispersion was stopped and the use of the silicone oil emulsion was stopped. The volume-based median diameter of the obtained toner 7 was 5.4 μm.

<Production Example of Toner 8>
Toner 8 was obtained in the same manner as in the production example of toner 2 except that the crosslinked resin fine particle B2 dispersion was changed to the crosslinked resin fine particle B3 dispersion. The obtained toner 8 had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 9>
A toner 9 was obtained in the same manner as in the production example of the toner 2 except that the crosslinked resin fine particle B2 dispersion was changed to the crosslinked resin fine particle B4 dispersion. The obtained toner 9 had a volume-based median diameter of 5.5 μm.

<Production Example of Toner 10>
A toner 10 was obtained in the same manner as in the production example of the toner 2 except that the crosslinked resin fine particle B2 dispersion was changed to the crosslinked resin fine particle B5 dispersion. The resulting toner 10 had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 11>
A toner 11 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A3 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B6 dispersion. The volume-based median diameter of the obtained toner 11 was 7.8 μm.

<Production Example of Toner 12>
A toner 12 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A4 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B7 dispersion. The toner 12 thus obtained had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 13>
A toner 13 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A5 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B8 dispersion. The obtained toner 13 had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 14>
A toner 14 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A6 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B9 dispersion. The volume-based median diameter of the obtained toner 14 was 5.5 μm.

<Production Example of Toner 15>
Toner 15 was obtained in the same manner as in the production example of toner 1 except that resin fine particle A1 dispersion was changed to resin fine particle A7 dispersion and cross-linked resin fine particle B1 dispersion was changed to cross-linked resin fine particle B10 dispersion. The resulting toner 15 had a volume-based median diameter of 5.5 μm.

<Production Example of Toner 16>
Toner 16 was obtained in the same manner as in the production example of toner 1 except that the resin fine particle A1 dispersion was not used and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B11 dispersion. The volume-based median diameter of the obtained toner 16 was 5.5 μm.

<Production Example of Toner 17>
Toner 2 except that the amount of resin fine particle A2 dispersion used was changed to 487.5 parts, the amount of crosslinked resin fine particle B2 dispersion was changed to crosslinked resin fine particle B12 dispersion, and the amount used was changed to 12.5 parts. Toner 17 was obtained in the same manner as in the above production example. The obtained toner 17 had a volume-based median diameter of 5.4 μm.

<Production Example of Comparative Toner 1>
Comparative toner 1 was obtained in the same manner as in the production example of toner 11 except that the crosslinked resin fine particle B6 dispersion was not used. The volume-based median diameter of the obtained comparative toner 1 was 7.6 μm.

<Production Example of Comparative Toner 2>
Except for changing the crosslinked resin fine particle B6 dispersion to the resin fine particle B6 dispersion (in the production example of the crosslinked resin fine particle B6 dispersion, the concentration of the resin fine particle B6 is 20% aqueous dispersion before the crosslinking treatment). Comparative toner 2 was obtained in the same manner as in Production Example. The volume-based median diameter of the obtained comparative toner 2 was 7.8 μm.

<Production Example of Comparative Toner 3>
Comparative toner 3 was obtained in the same manner as in the production example of toner 11 except that the crosslinked resin fine particle B6 dispersion was changed to the crosslinked resin fine particle B13 dispersion. The volume-based median diameter of the obtained comparative toner 3 was 8.2 μm.

<Production Example of Comparative Toner 4>
A comparative toner 4 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A8 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B14 dispersion. . The obtained reference toner 4 had a volume-based median diameter of 6.2 μm.

<Production Example of Comparative Toner 5>
A comparative toner 5 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle A1 dispersion was changed to the resin fine particle A9 dispersion and the crosslinked resin fine particle B1 dispersion was changed to the crosslinked resin fine particle B15 dispersion. . The volume-based median diameter of the obtained comparative toner 5 was 5.5 μm.

<Production Example of Comparative Toner 6>
-Resin fine particle A10 dispersion 375 parts-Crosslinked resin fine particle B16 dispersion 125 parts-Colorant fine particle dispersion 80 parts-Aliphatic hydrocarbon fine particle dispersion 50 parts-Ion exchange water 310 parts The above materials are made of round stainless steel After charging and mixing in the flask, 60 parts 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 rotation speed so that the mixed solution was stirred.
After holding at 73 ° C. for 20 minutes, it was confirmed that the volume-based median diameter of the formed aggregate particles was about 6.0 μm.
After adding 340 parts of 5% ethylenediamine tetraacetate aqueous solution to the dispersion containing the aggregate particles, the mixture was heated to 98 ° C. while stirring was continued. Then, the aggregate particles were fused by maintaining at 98 ° C. for 1 hour.
Thereafter, the mixture was cooled to 25 ° C., filtered and solid-liquid separated, and then washed with ion exchange water.
After completion of washing, the toner was dried using a vacuum dryer to obtain comparative toner particles 6 having a volume-based median diameter of 5.4 μm.
100 parts of the comparative toner particles 6 are subjected to a hydrophobization treatment in which 1.5 parts of silica fine particles hydrophobized with a primary particle number average particle size of 10 nm and a primary particle number hydrophobization treatment with a number average particle size of 100 nm are applied. Comparative toner 6 was obtained by dry-mixing 2.5 parts of silica fine particles with a Henschel mixer (Mitsui Mine).

<Production Example of Comparative Toner 7>
A comparative toner 7 was obtained in the same manner as in the production example of the comparative toner 6 except that the resin fine particle A10 dispersion was changed to the resin fine particle A11 dispersion and the crosslinked resin fine particle B16 dispersion was not used. The obtained reference toner 7 had a volume-based median diameter of 5.4 μm.

<Examples 1-17 and Comparative Examples 1-7>
The following evaluation tests were performed using toners 1 to 17 and comparative toners 1 to 7. The evaluation results are shown in Tables 4-1 and 4-2.

<Evaluation of low-temperature fixability>
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 (0.75 mg / cm ² ) on the 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 modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using the fixing unit.
In an environment of room temperature 15 ° C. and humidity 10% RH, the process speed is set to 357 mm / second,
The appearance when the unfixed toner image was fixed was visually evaluated.
A: Fixing is possible at a temperature of 140 ° C. or lower B: Fixing is possible at a temperature higher than 140 ° C. and 150 ° C. or lower C: Fixing is possible at a temperature higher than 150 ° C.

<Evaluation of hot offset resistance>
The two-component developer prepared in “Evaluation of low-temperature fixability” was used.
For the evaluation, a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) was used, and an unfixed toner image (0.1 mg / cm ² ) was formed on the 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 modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using the fixing unit.
The process speed was set to 357 mm / sec in a room temperature 23 ° C. humidity 5% RH environment, and the appearance when the unfixed toner image was fixed was visually evaluated. Specifically, the occurrence of hot offset was determined based on the presence or absence of adhesion of toner that attempted fixing under the above conditions to the fixing roller.
A: Hot offset occurs at a temperature higher than 160 ° C., or hot offset does not occur up to 200 ° C. B: Hot offset occurs at a temperature higher than 140 ° C. and lower than 160 ° C. C: Higher than 130 ° C. and lower than 140 ° C. Hot offset occurs at temperatures of D: Hot offset occurs at temperatures below 130 ° C

<Evaluation of charge retention>
0.01 g of toner was weighed into an aluminum pan and charged to −600 V using a scorotron charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface potential meter (model 347 manufactured by Trek Japan) in an atmosphere of a temperature of 30 ° C. and a humidity of 80% RH.
From the measurement results, the charge retention was calculated from the following equation. The charge retention was evaluated based on the charge retention.
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%

<Evaluation of storage stability (blocking resistance)>
The toner was allowed to stand for 3 days in a constant temperature and humidity chamber having a temperature of 50 ° C. and a humidity of 50% RH, and the degree of blocking was visually evaluated.
A: Blocking does not occur, or even if blocking occurs, it disperses easily by light vibration. B: Blocking occurs, but disperses if it continues to vibrate. C: Blocking occurs. Even if force is applied, it does not disperse.

<Evaluation of eraser resistance>
The toner was fixed in the same manner as in “Evaluation of low-temperature fixability”. Then, the erasure resistance of the fixed material at a fixing temperature of 155 ° C. was tested using an eraser (product name: MONO, manufactured by Dragonfly Pencil Co., Ltd.).
A: Not erased with eraser B: Image density is reduced by erasing with eraser C: Erased with eraser

<Glossiness evaluation>
The toner was fixed by the same method as the low temperature fixability evaluation method. The 60 ° gloss at a fixing temperature of 140 ° C. was measured using a gloss meter (product name: VG7000, manufacturer, Nippon Denshoku Industries Co., Ltd.).
A: Gloss 10 or more B: Gloss 5 or more and less than 10 C: Gloss less than 5 or cannot be fixed at 140 ° C.

表中のＸは「樹脂成分中の不飽和結合を有する脂肪族炭化水素樹脂の架橋体の含有量（質量％）」を、Ｙは「樹脂成分１００質量部に対する脂肪族炭化水素の質量部数」を、Ｚは「樹脂成分１００質量部に対するシリコーンオイルの質量部数」をそれぞれ示す。

X in the table is “the content (mass%) of a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond in the resin component”, and Y is “the number of parts of the aliphatic hydrocarbon relative to 100 parts by mass of the resin component”. , Z represents “the number of parts by mass of silicone oil relative to 100 parts by mass of the resin component”, respectively.

Claims (17)

A toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the following formula (1);
Having at least one monomer unit Y2 selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3);
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
The toner, wherein the content of the monomer unit Y2 is 3% by mass or more and 35% by mass or less with respect to the total mass of the ester group-containing olefin copolymer.

(In the formulas (1) to (3), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or CH ₃ represents R ⁵ represents CH ₃ or C ₂ H ₅ The total mass of the ester group-containing olefin copolymer is W,
The mass of the monomer unit represented by the formula (1) is l,
The mass of the monomer unit represented by the formula (2) is m,
When the mass of the monomer unit represented by the formula (3) is n,
The toner according to claim 1, wherein a value of (l + m + n) / W in the ester group-containing olefin copolymer contained in the resin component is 0.80 or more.   Content of the crosslinked body of the aliphatic hydrocarbon resin which has the said unsaturated bond is 1.0 mass% or more and 8.0 mass% or less with respect to the total mass of a resin component. Toner.   The toner according to claim 1, wherein the aliphatic hydrocarbon resin having an unsaturated bond is polybutadiene.   The toner according to claim 4, wherein the polybutadiene has a weight average molecular weight of 10,000 to 300,000. The polybutadiene has a 1,2-polybutadiene structure;
The content ratio of the 1,2-polybutadiene structure in the polybutadiene is 70% by mass or more,
The toner according to claim 4, wherein 50% by mass or more of the 1,2-polybutadiene structure is a syndiotactic structure.   The toner according to claim 4, wherein the polybutadiene has a melting point of 60 ° C. or higher and 80 ° C. or lower.   The toner according to claim 1, wherein the resin component further contains at least one of an ethylene-methacrylic acid copolymer and an ethylene-acrylic acid copolymer. The ester group-containing olefin copolymer is
2. An ester group-containing olefin copolymer A having a softening point of 120 ° C. or higher and 160 ° C. or lower and an ester group-containing olefin copolymer B having a softening point of 70 ° C. or higher and 100 ° C. or lower are contained. The toner according to any one of 1 to 8. The toner particles contain an aliphatic hydrocarbon having a melting point of 50 ° C. or higher and 100 ° C. or lower,
The toner according to claim 1, wherein a content of the aliphatic hydrocarbon is 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin component. The toner particles contain silicone oil,
The toner according to claim 1, wherein a content of the silicone oil is 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component.   The toner according to claim 1, wherein the ester group-containing olefin copolymer is an ethylene-vinyl acetate copolymer. A method for producing a toner having toner particles containing a resin component,
The resin component contains an ester group-containing olefin copolymer and a crosslinked product of an aliphatic hydrocarbon resin having an unsaturated bond,
A preparation step of preparing a resin fine particle dispersion in which the resin fine particles for producing the resin component are dispersed in an aqueous medium; and
A crosslinking step of crosslinking the aliphatic hydrocarbon resin having an unsaturated bond present in the resin fine particles using a crosslinking agent;
The ester group-containing olefin copolymer is
Monomer unit Y1 represented by the following formula (1);
Having at least one monomer unit Y2 selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3);
The content of the ester group-containing olefin copolymer contained in the resin component is 50% by mass or more based on the total mass of the resin component,
A method for producing a toner, wherein the content of the monomer unit Y2 is 3% by mass or more and 35% by mass or less with respect to the total mass of the ester group-containing olefin copolymer.

(In the formulas (1) to (3), R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , and R ⁴ represents H or CH ₃ represents R ⁵ represents CH ₃ or C ₂ H ₅ After the preparation step of preparing the resin fine particle dispersion,
An aggregation step of aggregating the resin fine particles to form aggregate particles, and
And further comprising a fusing step of fusing the aggregate particles by heating,
Between the preparation step of preparing the resin fine particle dispersion and the aggregation step, the crosslinking step is used to convert the aliphatic hydrocarbon resin having the unsaturated bond present in the resin fine particles. The method for producing a toner according to claim 13, which is a step of crosslinking. The ester group-containing olefin copolymer is an ethylene-vinyl acetate copolymer,
The method for producing a toner according to claim 13, wherein the aliphatic hydrocarbon resin having an unsaturated bond is polybutadiene. The resin fine particles are
Resin fine particles A and resin fine particles B,
The resin fine particle A contains an ester group-containing olefin copolymer, does not contain an aliphatic hydrocarbon resin having an unsaturated bond,
The resin fine particle B contains an ester group-containing olefin copolymer and an aliphatic hydrocarbon resin having an unsaturated bond, and the volume-based median diameter of the resin fine particle B is 50 nm or more and 1000 nm or less,
The crosslinking step is an aliphatic group having the unsaturated bond present in the resin fine particles B by using the cross-linking agent between the end of the preparation step for preparing the resin fine particle dispersion and the start of the aggregation step. A step of crosslinking the hydrocarbon resin,
The toner production method according to claim 14, wherein the aggregation step is a step of aggregating the resin fine particles A and the resin fine particles B having undergone the crosslinking step to form aggregate particles.   The content of the aliphatic hydrocarbon resin having an unsaturated bond in the resin fine particle B is 5% by mass or more and 20% by mass or less with respect to the total amount of the resin constituting the resin fine particle B. Toner production method.