JP2018084742A - Toner and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that is excellent in low-temperature fixability, storage durability at high temperature, charge holding property, and hot offset resistance.SOLUTION: A toner includes toner particles containing a resin component and silicone oil. The resin component includes a modified polyolefin cross-linked body that is a reactant of a cross-linking agent and an olefin-based acid radical-containing copolymer having a carboxy group with an acid value of 50 to 300 mgKOH/g or less, and an olefin-based ester group-containing copolymer. The olefin-based ester group-containing copolymer includes specific monomer units Y1 and Y2; the content of the olefin-based ester group-containing copolymer is 50 mass% or more relative to the total mass of the resin component, and the content of the monomer unit Y2 is 3 mass% or more and 35 mass% or less relative to the total mass of the olefin-based ester group-containing copolymer; the cross-linking agent includes, in a molecule, two or more groups selected from an oxazoline group and a carbodiimide group.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system and a method for producing the same.

2. Description of the Related Art In recent years, with the increasing demand for energy saving during image formation, efforts have been made to further lower the toner fixing temperature. As one of the methods for improving the low-temperature fixability, there has been proposed a technique using a crystalline polyester resin having 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 10). ).

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

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

On the other hand, when these olefinic ester group-containing copolymers are used as the main resin of the toner as described in Patent Documents 9 and 10, there is a problem that the hot offset resistance is lowered. In order to cope with the above-mentioned problems, the present inventors tried to use a high molecular weight resin that is generally known to improve the hot offset resistance. However, because the olefinic ester group-containing copolymer has low polarity and low intermolecular force, the hot offset resistance is improved even when the olefinic ester group-containing copolymer and high molecular weight resin are used in combination. I couldn't make it.
Accordingly, an object of the present invention is to provide a toner having excellent low-temperature fixability, storage resistance at high temperatures, charge retention, and hot offset resistance.

As a result of intensive studies by the present inventors, ethylene (propylene) -acetate copolymer such as ethylene-vinyl acetate copolymer, ethylene (propylene) -acrylic acid such as ethylene-methyl acrylate, etc. A specific olefinic ester group-containing copolymer including an ester copolymer, an ethylene (propylene) -methacrylic acid ester copolymer such as ethylene-methyl methacrylate, and a mixture thereof is used as a main resin. In addition, a olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less and a modified polyolefin crosslinked body made of a resin reacted with a crosslinking agent are used in combination. By using silicone oil as a low temperature fixability, storage resistance at high temperatures, charge retention, and hot resistance It has been found that toner having excellent offset resistance is obtained.
Although the main resin has a high crystallinity despite its low glass transition temperature, it has good blocking properties at high temperatures. However, when other resins are added and dissolved, the crystallinity decreases. However, it has the subject that blocking property falls.

However, the modified polyolefin cross-linked product does not inhibit the crystallization of the olefin-based ester group-containing copolymer due to the similarity of the chemical structure, so that the blocking property is not lowered. Furthermore, when a high temperature is applied during fixing in the electrophotographic process, the modified polyolefin cross-linked product is compatible with the chemical structure similar to the main resin and spreads inside the toner, and molecular entanglement occurs due to the cross-linked structure. Therefore, it is considered that the hot offset resistance can be improved.
In addition, it is known that a release agent is used to improve hot offset resistance. However, an olefinic ester group-containing copolymer is generally different from a release agent generally used for toner, such as an alkyl wax. High solubility. For this reason, when a release agent generally used for toner is used, the release agent is compatible with the olefinic ester group-containing copolymer during toner fixing, so that it does not easily leak out. It cannot be made.
On the other hand, since silicone oil is incompatible with the olefin ester group-containing copolymer, when used as a mold release agent, it sufficiently oozes out of the toner at the time of toner fixing, thus improving hot offset resistance. it can. However, when the silicone oil is contained in the toner, the silicone oil oozes out from the toner surface layer, so that there is a problem that the preservability during long-term storage under high temperature and high humidity is lowered. However, it has been found that the inclusion of a modified polyolefin cross-linked product can suppress the seepage of silicone oil during toner preparation and improve the storage stability during long-term storage.
The reason for this is not clear, but the cross-linking point of the modified polyolefin cross-link has a hydrophilic amide ester bond, and the exfoliation to the outside is suppressed by covering the periphery of the hydrophobic polyolefin oil. It is thought that it is because it is doing.

That is, the toner of the present invention is
A toner comprising toner particles containing a resin component and silicone oil,
The resin component is
A modified polyolefin crosslinked product which is a reaction product of an olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less, and a crosslinking agent;
An olefinic ester group-containing copolymer;
Have
The olefin-based ester group-containing copolymer is
Monomer unit Y1 represented by the following formula (1);
At least one monomer unit Y2 selected from the group of monomer units represented by the following formula (2) and monomer units represented by the following formula (3);
Have
The content of the olefinic ester group-containing copolymer in the resin component is 50% by mass or more based on the total mass of the resin component,
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 olefinic ester group-containing copolymer.
The toner, wherein the crosslinking agent has two or more groups selected from an oxazoline group and a carbodiimide group in the molecule.

(Where R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is CH ₃ or C ₂ H ₅ , R ⁴ is H or CH ₃ , R ⁵ is CH ₃ or C ₂ H ₅ )
The present invention also relates to a method for producing a toner comprising toner particles containing a resin component and silicone oil,
Including a preparation step of preparing a resin fine particle dispersion in which the resin fine particles for generating the resin component are dispersed in an aqueous medium,
The resin component is
A modified polyolefin crosslinked product which is a reaction product of an olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less, and a crosslinking agent;
An olefinic ester group-containing copolymer;
Have
The olefin-based ester group-containing copolymer is
Monomer unit Y1 represented by the formula (1);
At least one monomer unit Y2 selected from the group of monomer units represented by formula (2) and monomer units represented by formula (3);
Have
The content of the olefinic ester group-containing copolymer in the resin component is 50% by mass or more based on the total mass of the resin component,
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 olefinic ester group-containing copolymer.
The present invention relates to a method for producing a toner, wherein the crosslinking agent has two or more groups selected from an oxazoline group and a carbodiimide group in the molecule.

  According to the present invention, it is possible to provide a toner having excellent low-temperature fixability, storage resistance at high temperatures, charge retention, and hot offset resistance.

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).
In the present invention, the resin component means a polymer component mainly contributing to fixing performance. The resin component includes an olefinic ester group-containing copolymer and a modified polyolefin crosslinked product. The olefinic ester group-containing copolymer is a polymer in which a monomer unit containing an ester group is introduced into a polyolefin skeleton by means of copolymerization or the like. Specifically, at least one monomer unit selected from the group of the monomer unit Y1 represented by the following formula (1), the monomer unit represented by the following formula (2), and the monomer unit represented by the following formula (3) Y2.

Hereinafter, the monomer unit represented by the formula (2) and at least one monomer unit Y2 selected from the group of monomer units represented by the formula (3) will be specifically described.
The olefin ester group-containing copolymer has a monomer unit represented by the formula (1) and a monomer unit represented by the formula (2), wherein R ¹ is H, R ² is H, R ³ It is preferable to contain an ethylene-vinyl acetate copolymer in which is CH ₃ . Thereby, since the melting point can be designed low, the low-temperature fixability is improved.
The olefin ester group-containing copolymer is
An ethylene-methyl acrylate copolymer having a monomer unit represented by the formula (1) and a monomer unit represented by the formula (3), wherein R ¹ is H, R ⁴ is H, and R ⁵ is CH ₃ ,
An ethylene-ethyl acrylate copolymer having a monomer unit represented by the formula (1) and a monomer unit represented by the formula (3), wherein R ¹ is H, R ⁴ is H, and R ⁵ is C ₂ H _5. A polymer or ethylene-methacrylic acid having a monomer unit represented by the formula (1) and a monomer unit represented by the formula (3), wherein R ¹ is H, R ⁴ is CH ₃ , and R ⁵ is CH ₃ It is preferable to contain an acid methyl copolymer. Storage stability under high temperature and high humidity is improved due to high chemical stability.

One or more olefinic ester group-containing copolymers may be contained in the resin component.
The total mass of the olefinic ester group-containing copolymer is W, and the masses of the monomer units represented by formula (1), formula (2), and formula (3) are l, m, and n, respectively. The value of (l + m + n) / W of the olefin ester group-containing copolymer contained in the resin component is preferably 0.80 or more from the viewpoint of charge retention and blocking properties. It is more preferably 0.95 or more, and further preferably 1.00.
In addition to the monomer unit Y1 and the monomer unit Y2, the olefin ester group-containing copolymer may have a monomer unit. Although it will not specifically limit if the effect of this invention is not impaired, For example, the monomer unit shown by Formula (4) and the monomer unit shown by Formula (5) are mentioned. These may be introduced by adding a corresponding monomer in the copolymerization reaction for producing the olefinic ester group-containing copolymer, or by modifying the olefinic ester group-containing copolymer by a polymer reaction. it can.

However, from the viewpoint of charge retention, the acid value of the olefin ester group-containing copolymer is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and substantially 0 mgKOH / g. More preferably.
Content of an olefin type ester group containing copolymer is 50 mass% or more with respect to the total mass of a resin component. The content of 70% by mass or more is preferable from the viewpoint of low-temperature fixability. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less.
The glass transition temperature of the olefin-based ester group-containing copolymer is preferably 0 ° C. or less, and when it is contained in the resin component by 50% by mass or more, the low-temperature fixability is improved.

The content of the monomer unit Y2 needs to be 3% by mass or more and 35% by mass or less with respect to the total mass of the olefinic ester group-containing copolymer. From 5% by weight to 20% by weight, it is preferable from the viewpoint of charge retention.
When the content of the monomer unit Y2 in the olefin ester group-containing copolymer is 35% by mass or less, the charge retention as a toner is improved. On the other hand, when the 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 unit and the content of the monomer unit Y2 can be measured using a general analysis method, such as nuclear magnetic resonance (NMR) or pyrolysis gas chromatography. This method can be applied.

Hereinafter, a measurement method using ¹ H-NMR will be described. Integral ratio of hydrogen atom of alkylene represented by monomer unit (1), hydrogen atom of acetyl group represented by monomer unit (2), methyl group bonded to oxygen represented by monomer unit (3), or hydrogen atom of ethylene group The content ratio of each monomer unit can be calculated by comparing each.
Specifically, the content ratio of each monomer unit in the ethylene-vinyl acetate copolymer is calculated as follows. A solution prepared by dissolving about 5 mg of a sample in 0.5 ml of heavy acetone containing tetramethylsilane as an internal standard of 0.00 ppm is placed in a sample tube, and the repetition time is 2.7 seconds and the number of integrations is 16 times. ¹ H-NMR measurement is performed. Since the peak at 1.14 to 1.36 ppm corresponds to CH ₂ —CH ₂ of the ethylene unit and the peak near 2.04 ppm corresponds to CH ₃ of the vinyl acetate unit, the ratio of the integrated values of these peaks is calculated. And the content ratio is calculated.

Two or more types of olefin ester group-containing copolymers are preferably contained. The softening point (Tm) in the flow tester measurement of at least one olefinic ester group-containing copolymer is 120 ° C. or higher and 160 ° C. or lower (more preferably 120 ° C. or higher and 150 ° C. or lower), and in the at least one flow tester measurement The softening point is preferably 70 ° C. or higher and 100 ° C. or lower (more preferably 70 ° C. or higher and 90 ° C. or lower).
It is preferable that a resin having a softening point of 120 ° C. or higher and 160 ° C. or lower is included from the viewpoint of enduring impact and pressure when using the toner, and a resin having a softening point of 70 ° C. or higher and 100 ° C. or lower is preferable from the viewpoint of image gloss. It is preferably contained.
The content of the olefinic ester group-containing copolymer having a softening point of 120 ° C. or higher and 160 ° C. or lower is 40% by mass or more and 80% by mass or less based on the total mass of the resin component. It is preferable from the viewpoint of withstanding impact and pressure. On the other hand, the glossiness of the image is such that the content of the olefinic ester group-containing copolymer having a softening point of 70 ° C. or more and 100 ° C. or less is 10% by mass or more and 30% by mass or less with respect to the total mass of the resin component. From the viewpoint of

The softening point (Tm) in the flow tester measurement can be controlled by changing the molecular weight of the olefinic ester group-containing copolymer, and the softening point can be increased by increasing the molecular weight.
The softening point in the flow tester measurement can be measured using a load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation).
The CFT-500D melts while raising the temperature of the measurement sample filled in the cylinder while applying a constant load with the piston from the top and pushes it out from the narrow tube hole at the bottom of the cylinder. It is an apparatus that can graph a flow curve from 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 lowering amount is the sum of X and Smin is defined as the melting temperature in the 1/2 method.
As a measurement sample, 1.2 g of a sample is compression-molded at 25 MPa in an environment of 25 ° C. using a tablet molding compressor (for example, a standard manual Newton press NT-100H, manufactured by NP System Co., Ltd.) for 60 seconds. 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 olefin ester group-containing 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 breaking elongation is measured under conditions based on JIS K 7162. When a plurality of the olefinic ester group-containing copolymers are contained in the resin component, the measurement is performed under the above conditions after melt mixing.

The toner particles include, as a resin component, an olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less and a modified polyolefin crosslinked product which is a reaction product of a crosslinking agent. The modified polyolefin crosslinked product can be obtained by reacting an olefinic acid group-containing copolymer and a crosslinking agent.
The olefinic acid group-containing copolymer constituting the modified polyolefin cross-linked product needs to have a carboxy group, and the carboxy group functions as a reaction site of a cross-linking agent described later. From the viewpoint of easy crosslinking reaction with the crosslinking agent, the acid value of the olefinic acid group-containing copolymer needs to be 50 mgKOH / g or more, and from the viewpoint of charge retention, it needs to be 300 mgKOH / g or less. is there. Preferably they are 80 mgKOH / g or more and 200 mgKOH / g or less.

The olefinic acid group-containing copolymer is derived from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, etc. so that the main component is a polyolefin such as polyethylene or polypropylene, and further has an acid group. It is a polymer in which a monomer unit is introduced by means such as copolymerization.
Moreover, as long as the physical properties are not affected, a monomer unit other than polyolefin or the monomer unit having an acid group may be included. The content of the monomer unit other than the polyolefin and the monomer unit having an acid group is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass in the olefinic acid group-containing copolymer. It is particularly preferable that the content is substantially 0% by mass. From the viewpoint of having a structural similarity and being easily mixed with the olefinic ester group-containing copolymer in the toner and improving the hot offset resistance, the olefinic acid group-containing copolymer may be ethylene-acrylic acid. A copolymer or an ethylene-methacrylic acid copolymer is preferred.

The olefinic acid group-containing copolymer preferably has a melt flow rate of 400 g / 10 min or less from the viewpoint of storage stability. From the viewpoint of entanglement with the olefinic ester group-containing copolymer in the toner even after the modified polyolefin crosslinked body is formed, the melt flow rate is preferably 10 g / 10 min or more. As a result, strain hardening due to entanglement with the olefinic ester group-containing copolymer tends to occur inside the toner at the time of fixing the toner, and as a result, the hot offset resistance is improved.
The melt flow rate is a value indicating the fluidity at the time of melting of the thermoplastic material, and is measured under conditions of 190 ° C. and 2160 g load based on JIS K 7210. The melting point of the olefinic acid group-containing copolymer is preferably 50 ° C. or higher and 100 ° C. or lower from the viewpoint of low-temperature fixability and storage stability. When the melting point is 100 ° C. or lower, the low-temperature fixability is further improved. Further, when the melting point is 90 ° C. or lower, the low-temperature fixability is further improved. On the other hand, when the melting point is 50 ° C. or higher, the storage stability is improved.

The cross-linking agent is not particularly limited as long as it contains two or more groups selected from oxazoline groups and carbodiimide groups which are cross-linking reactive groups in the molecule and forms an amide ester bond with a carboxy group. It is preferable that the crosslinking agent has two or more oxazoline groups or carbodiimide groups in the molecule. From the viewpoint of easy entanglement with the olefinic ester group-containing copolymer at the time of fixing the toner, a polymer having a crosslinking reactive group (crosslinked polymer) is preferable. Crosslinking agents containing the above oxazoline groups are preferred.
The cross-linked polymer has two or more groups selected from oxazoline group and carbodiimide group in the molecule and reacts well with the carboxy group of the olefinic acid group-containing copolymer to form a stable amide ester bond after the reaction. To do. When the modified polyolefin cross-linked product is entangled with the olefinic ester group-containing copolymer at the time of fixing the toner, the strain-hardening property is exhibited, thereby improving the hot offset resistance.
In the toner of the present invention, it is necessary to use a silicone oil described later as a release agent. When a modified polyolefin cross-linked product is used, it is possible to improve the storage stability during long-term storage when silicone oil is used as a release agent. The reason for this is considered to be that the hydrophobic silicone oil is covered with a hydrophilic amide ester bond to prevent the toner from oozing out of the toner.

  The number average molecular weight of the polymer having a crosslinking reactive group is preferably 5,000 or more and 500,000 or less from the viewpoint of increasing the reactivity with the olefinic acid group-containing copolymer. As the oxazoline group-containing polymer, a polymer having an acrylic skeleton as a main chain, a polymer having a styrene / acryl skeleton as a main chain, a polymer having a styrene skeleton as a main chain, and a polymer having an acrylonitrile / styrene skeleton as a main chain can be used.

The crosslinking agent is preferably a polymer containing an oxazoline group. The oxazoline value of the oxazoline group-containing polymer is preferably 150 g-solid / eq or more and 400 g-solid / eq or less, and 200 g-solid / eq from the viewpoint of improving the hot offset resistance while maintaining the low-temperature fixability of the toner. More preferably, it is eq or more and 400 g-solid / eq or less.
The oxazoline value (g-solid / eq.) Is a polymer mass per mol of the oxazoline group, and can be determined by measuring a nuclear magnetic resonance spectrum ( ¹ H-NMR).
Specifically, about 30 mg of a polymer containing an oxazoline group is dissolved in CDCl ₃ to obtain an oxazoline group-containing polymer-CDCl ₃ solution in a sample tube having a diameter of 5 mm. The solution was measured using a Fourier transform nuclear magnetic resonance apparatus (JNM-EX400, manufactured by JEOL Ltd.), measurement frequency: 400 MHz, pulse condition: 5.0 μs, measurement temperature: 60
The content of the oxazoline group in the oxazoline group-containing polymer can be measured by measuring the ¹ H-NMR spectrum under the condition of ° C.

  Further, the modified polyolefin cross-linked product, which is a reaction product of the olefinic acid group-containing copolymer having a carboxy group and the cross-linking agent, is dispersed in the toner particles in the form of fine particles having a weight average particle size of 10 nm to 1000 nm. Is preferred. When the thickness is 10 nm or more, the glossiness of the image is improved, and when the thickness is 1000 nm or less, the hot offset resistance is improved. In order to disperse the crosslinked product in the form of fine particles of 10 nm or more and 1000 nm or less in the toner, it is preferable to produce a fine particle crosslinked product of 10 nm or more and 1000 nm or less, and to produce by a later-described emulsion aggregation method.

Moreover, it is preferable that content of a modified polyolefin crosslinked body is 1 to 8 mass% with respect to the total mass of a resin component. More preferably, it is 1 to 3 mass%. When the content is 1% by mass or more, the effect of hot offset resistance is enhanced, and when the content is 8% by mass or less, low-temperature fixability and glossiness are improved.

In the toner of the present invention, as the resin component, in addition to the olefin ester group-containing copolymer and the modified polyolefin crosslinked product, other polymers may be used in combination. Specifically, the following polymers can be used.
Styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Styrene copolymers such as acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic resins, acrylic resins, methacrylic resins, poly Examples thereof include vinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, and polypropylene resin.
The toner particles preferably contain an olefinic acid group-containing copolymer having an uncrosslinked carboxy group as a resin component. The acid group of the olefinic acid group-containing copolymer forms a hydrogen bond with the hydroxyl group on the paper surface, the adhesion between the toner and the paper is increased, and the eraser resistance of the fixed product is improved. Among the olefinic acid group-containing copolymers, the ethylene methacrylic acid copolymer or the ethylene acrylic acid copolymer has a higher melting point than the olefinic ester group-containing copolymer. The shelf life of the product is improved. Further, from the structural similarity, it is preferable for entangled with the olefinic ester group-containing copolymer in the toner to improve hot offset resistance.

  The content of the olefinic acid group-containing copolymer (preferably ethylene methacrylic acid copolymer or ethylene acrylic acid copolymer) is preferably 10% by mass or more and 50% by mass or less with respect to the total mass of the resin component. More preferably, it is at least 30% by mass. Adhesiveness with paper becomes favorable as it is 10 mass% or more. In addition, when it is 30% by mass or less, the environmental fluctuation of the charging property is reduced.

The acid value of the olefinic acid group-containing copolymer (preferably ethylene methacrylic acid copolymer or ethylene acrylic acid copolymer) is preferably from 50 mgKOH / g to 300 mgKOH / g, more preferably from 80 mgKOH / g to 200 mgKOH / g. preferable. When the acid value is 50 mgKOH / g or more, sufficient adhesion to paper is exhibited, and when it is 300 mgKOH / g or less, the chargeability is improved.
The acid value is the number of mg of potassium hydroxide required to neutralize acid components such as free fatty acids and resin acids contained in 1 g of a sample. The measurement method is as follows according to JIS-K0070.

(1) Reagent / solvent: Toluene-ethyl alcohol mixture (2: 1) is neutralized with 0.1 mol / L potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.
Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 mL of ethyl alcohol (95% by volume).
-0.1 mol / L potassium hydroxide ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95% by volume) to 1 L, leave it for 2 to 3 days, and filter. The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).
(2) Operation Weigh correctly 1 to 20 g of resin as a sample, add 100 mL of the solvent and a few drops of the phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with the above 0.1 mol / L potassium hydroxide ethyl alcohol solution, and the end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(3) Calculation formula The acid value is calculated by the following formula.
A = B × f × 5.661 / S
A: Acid value (mgKOH / g)
B: Amount of use of 0.1 mol / L potassium hydroxide ethyl alcohol solution (mL)
f: Factor of 0.1 mol / L potassium hydroxide ethyl alcohol solution S: Sample (g)

  The softening point in the flow tester measurement of the olefinic acid group-containing copolymer (preferably ethylene methacrylic acid or ethylene acrylic acid) is preferably 100 ° C. or higher. Thereby, blocking at the time of storage can be suppressed. On the other hand, the upper limit is preferably 140 ° C. or less from the viewpoint of adhesion between the toner and paper. When the softening point is 140 ° C. or less, it becomes easy to be compatible with the olefinic ester group-containing copolymer present in the toner, and the adhesion to paper is improved. The softening point in the flow tester measurement can be measured by the same method as the flow tester measurement of the olefinic ester group-containing copolymer described above.

The melting point of the olefinic acid group-containing copolymer used without crosslinking is preferably 50 ° C. or higher and 100 ° C. or lower from the viewpoint of low-temperature fixability and storage stability. When the melting point is 100 ° C. or lower, the low-temperature fixability is further improved. Further, when the melting point is 90 ° C. or lower, the low-temperature fixability is further improved. On the other hand, when the melting point is 50 ° C. or higher, the storage stability is improved.
Melting | fusing point of resin etc. can be measured using a scanning scanning calorimeter (DSC).
Specifically, a 0.01 to 0.02 g sample is precisely weighed in an aluminum pan, and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve.
From the obtained DSC curve, the peak temperature of the endothermic peak is defined as the melting point.

The toner particles contain silicone oil as a release agent. Release agents generally used for toners such as alkyl waxes tend to be compatible with the olefin ester group-containing copolymer, and the release effect is difficult to obtain. Further, the addition of silicone oil improves the dispersibility of the pigment in the toner and makes it easy to obtain a high density image.
When only the olefinic ester group-containing copolymer is used as the resin component, the silicone oil has a low affinity with the olefinic ester group-containing copolymer, and further, since it is a liquid, it is easily detached during toner production. However, when a modified polyolefin cross-linked product is used, it can be encapsulated in toner particles without detaching silicone oil during toner production. The reason for this is considered to be that the hydrophobic silicone oil is covered with a hydrophilic amide ester bond to prevent it from oozing out of the toner.

As the silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, carboxy-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil and the like can be used. The viscosity of the silicone oil is preferably 5 mm ² / S or more and 1000 mm ² / S or less, and more preferably 20 mm ² / S or more and 1000 mm ² / S or less.
The content of the silicone oil 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 in that good separability is obtained while suppressing a decrease in fluidity. More preferably, they are 5 to 25 mass parts.

Further, the toner particles have an aliphatic hydrocarbon compound having a melting point of preferably 50 ° C. or higher and 100 ° C. or lower (more preferably 60 ° C. or higher and 100 ° C. or lower) with respect to 100 parts by mass of the resin component. It is preferable to contain below part by mass.
When the aliphatic hydrocarbon compound is heated, the olefin ester group-containing copolymer can be plasticized. Therefore, by containing an aliphatic hydrocarbon compound in the toner particles, the olefin-based ester group-containing copolymer forming a matrix at the time of heat fixing of the toner is plasticized, and the low-temperature fixability can be improved.
Further, the aliphatic hydrocarbon compound having a melting point of 50 ° C. or more and 100 ° C. or less also acts as a nucleating agent for the olefinic ester group-containing copolymer. Therefore, the micro motility of the olefin ester group-containing copolymer is suppressed, and the chargeability is improved. The content of the aliphatic hydrocarbon compound is more preferably 10 parts 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 low temperature fixability and chargeability.
Specific examples of the aliphatic hydrocarbon compound include saturated hydrocarbons having 20 to 60 carbon atoms, such as hexacosane, triacontane, and hexatriacontane.

The toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan toner dyes include C.I. I. There is Solvent Blue 70.
Examples of the yellow toner pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.
These colorants can be used alone or in combination and further in 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.
It is preferable that content of a coloring agent is 1 to 20 mass parts with respect to 100 mass parts of resin components.

  Further, from the viewpoint of obtaining a high-definition image, the volume-based median diameter of the toner particles is preferably 3.0 μm or more and 10.0 μm or less, and more preferably 4.0 μm or more and 7.0 μm or less.

A method for producing toner particles will be described. The toner particles can be produced by any method. The method includes a preparation step of preparing a resin fine particle dispersion in which resin fine particles generating a resin component are dispersed in an aqueous medium. Further, granulating resin fine particles having an olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less in an aqueous medium, and in the aqueous medium of the resin fine particles, molecules It is preferable to include a step of adding a crosslinking agent having two or more groups selected from an oxazoline group and a carbodiimide group to obtain a modified polyolefin crosslinked product crosslinked by an amide ester bond.
By cross-linking the olefinic acid group-containing copolymer in the form of fine resin particles dispersed in an aqueous medium, a finely dispersed cross-linked product can be formed, which has good low-temperature fixability and improved hot offset resistance. Can be made.

Among the methods for producing toner particles in an aqueous medium, it is preferred that the toner particles are produced by an emulsion aggregation method described later, and a crosslinking reaction is carried out during the process. The emulsion aggregation method is a method for producing toner particles by preparing a resin fine particle dispersion sufficiently small with respect to a target particle diameter in advance and aggregating the resin fine particles in an aqueous medium.
In the emulsion aggregation method, after the preparation step of preparing the resin fine particle dispersion, the method further includes an aggregation step of aggregating the resin fine particles to form aggregate particles, and a fusion step of fusing the aggregate particles by heating. Is preferred. It is preferable to have a crosslinking step between the start of the resin fine particle dispersion preparation step and the end of the aggregation step. Hereinafter, the toner production method using the emulsion aggregation method will be specifically described, but the present invention is not limited thereto.

<Preparation process of resin fine particle dispersion>
This step is a step of preparing a resin fine particle dispersion in which resin fine particles that generate a resin component are dispersed in an aqueous medium. The resin fine particles can be produced by a known method, but are preferably produced by the following method.
In the present invention, it is preferable to prepare two resin fine particle dispersions A that do not contain a modified polyolefin crosslinked product and two resin fine particle dispersions B that contain a modified polyolefin crosslinked product. By using two resin fine particle dispersions, the dispersion state of the modified polyolefin crosslinked body in the toner can be controlled as described later, which is preferable from the viewpoint of hot offset resistance and glossiness.

The resin fine particle dispersion A is prepared as follows. The olefin ester group-containing 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.
Next, the organic solvent is preferably removed, and resin fine particles are dispersed to obtain a resin fine particle dispersion A. Moreover, it is preferable to dissolve both the olefin ester group-containing copolymer and the olefin acid group-containing copolymer (preferably ethylene methacrylic acid or ethylene acrylic acid) to form resin fine particles by a co-emulsification technique. By containing the olefinic acid group-containing copolymer, the reactivity of the fine particles in the emulsion aggregation method is increased and the particle size distribution of the toner is improved.

Further, the resin fine particle dispersion B is prepared as follows. The olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less 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. Next, the organic solvent is preferably removed, and the resin fine particles are dispersed to obtain a resin fine particle dispersion B.
In addition, it is preferable to dissolve the olefinic ester group-containing copolymer and the olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less to form resin fine particles by a co-emulsification technique. . The olefinic ester group-containing copolymer and olefinic acid group-containing copolymer are uniformly mixed in the atomized organic phase, improving the compatibility of the two in the toner and improving the hot offset resistance. To do.

More specifically, the olefinic ester group-containing copolymer and the olefinic acid group-containing copolymer are dissolved by heating in an organic solvent, and a surfactant or a basic compound is added. Subsequently, a co-emulsion liquid (resin fine particle dispersion) containing a resin is prepared by slowly adding an aqueous medium while applying shear with a homogenizer or the like. Alternatively, a co-emulsion liquid containing a resin is prepared by applying shearing with a homogenizer or the like after the addition of the aqueous medium. Then, the resin fine particle dispersion B is prepared by removing the organic solvent by heating or decompressing.
The amount ratio of the olefinic acid group-containing copolymer to 100 parts by mass of the olefinic ester group-containing copolymer in the resin fine particle dispersion B is preferably 5 parts by mass or more and 40 parts by mass or less. By setting the amount to 5 parts by mass or more, the reactivity of the olefinic acid group-containing copolymer is increased in the resin fine particles, and the crosslinking step described later proceeds smoothly. When the amount is 40 parts by mass or less, excessive reaction in the crosslinking step can be prevented, and the hot offset resistance of the toner is improved.

  In both resin fine particle dispersions A and B, the concentration of the resin component in the dispersion is preferably 10% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less. Any organic solvent that can dissolve the resin component can be used. A solvent having high solubility in an olefinic ester group-containing copolymer such as toluene, xylene, and ethyl acetate is preferred.

The surfactant used during the emulsification is not particularly limited. For example, sulfate anion surfactant, sulfonate salt, carboxylate salt, phosphate ester, soap anionic surfactant; amine salt type, quaternary ammonium salt type cationic surfactant, polyethylene glycol type, Examples thereof include alkylphenol ethylene oxide adduct-based and polyhydric alcohol-based nonionic surfactants.
Examples of the basic compound used during emulsification 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 average diameter of the resin fine particles is preferably from 50 nm to 1000 nm, and more preferably from 100 nm to 600 nm. When the average diameter is within the above range, toner particles having a desired particle diameter are easily obtained.
The volume-based average diameter of the resin fine particles B is preferably 50 nm or more and 1000 nm or less. By setting it within this range, the dispersion diameter of the crosslinked resin fine particles in the toner 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 average diameter can be measured with a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150, manufactured by Nikkiso).

<Crosslinking process>
The crosslinking step means that the resin fine particle dispersion contains two or more groups selected from oxazoline groups and carbodiimide groups in the molecule between the start of the resin fine particle dispersion preparation step and the end of the aggregation step described later. Modified polyolefin crosslinking by adding a crosslinking agent and forming an amide ester bond between the carboxy group of the olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less and the crosslinking agent It is a process of obtaining a body. It is preferable to provide a crosslinking step after the preparation step of the resin fine particle dispersion and before the aggregation step. By providing the crosslinking step in the above range, sufficiently small crosslinked fine particles having a uniform particle diameter can be formed, which is preferable from the viewpoint of low-temperature fixability and hot offset resistance.
Specifically, it is a step of adding a crosslinking agent to the resin fine particle dispersion B containing the olefinic acid group-containing copolymer and stirring the mixture to advance the crosslinking reaction.

As the cross-linking agent, there are oil-soluble and water-soluble ones, and either initiator may be used, but water-soluble is preferable from the viewpoint of reaction uniformity. The addition amount of the crosslinking agent is preferably 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the olefinic acid group-containing copolymer.
From the viewpoint of allowing the reaction to proceed efficiently, it is preferably heated to 70 ° C or higher, more preferably 80 ° C or higher, and even more preferably 90 ° C or higher. The heating time is preferably 1 hour or more and 12 hours or less. When the heating temperature and time are within the above ranges, the crosslinking reaction can be sufficiently advanced, and a good crosslinked structure can be obtained.

<Aggregation process>
In the aggregation step, the resin fine particle dispersion A and the resin fine particle dispersion B are mixed with a silicone oil emulsion, and if necessary, a colorant fine particle dispersion and an aliphatic hydrocarbon compound fine particle dispersion. Prepare. Next, the fine particles contained in the prepared mixed liquid are aggregated to form aggregate particles. As a method for forming aggregate particles, a method in which a flocculant is added and mixed in the above-mentioned mixed solution to increase the temperature, and mechanical power or the like is appropriately added can be preferably 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 dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure counter collision type dispersing machine, or the like is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.

The aliphatic hydrocarbon compound 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 counter collision type dispersing machine, or the like is preferably used. Further, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.
Examples of the aggregating agent 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; The polyvalent metal salts of From the viewpoint of particle size controllability in the aggregation process, a metal salt of a divalent metal such as calcium chloride or magnesium sulfate is preferred.

The addition and mixing of the flocculant is preferably performed in a temperature range of room temperature (25 ° C.) 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 average particle size of the aggregate particles formed in the aggregation process is not particularly limited, but is usually controlled to 4.0 to 7.0 μm so as to be the same as the average particle size of the toner particles to be obtained. Good. Control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition / mixing of the flocculant and the like and the conditions of the stirring and mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method.

<Fusion process>
The fusing step is a step of producing particles in which the agglomerated particle surface is smoothed by heating and fusing the agglomerated particles to a temperature equal to or higher than the melting point of the olefin ester group-containing 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 citrate and sodium citrate, both nitrilotriacetate (NTA) salts, COOH and OH There are many water-soluble polymers (polyelectrolytes) that contain the following functionalities.
The heating temperature may be not less than the melting point of the olefin ester group-containing copolymer contained in the aggregate particles and less than the temperature at which the olefin ester group-containing copolymer or olefin acid group-containing copolymer is thermally decomposed. That's fine. As the heating / fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the heating / fusion time depends on the temperature of heating and cannot be defined unconditionally, but is generally about 10 minutes to 10 hours.

<Cooling process>
In the cooling step, it is preferable to cool the temperature of the aqueous medium containing the resin particles obtained in the fusion step to a temperature lower than the crystallization temperature of the olefinic ester group-containing copolymer. By performing the cooling to a temperature lower than the crystallization temperature, generation of coarse particles can be suppressed. The specific cooling rate is preferably 0.1 to 50 ° C./min.
Further, it is preferable to perform annealing for promoting crystallization while maintaining the olefin ester group-containing copolymer at a high crystallization speed during or after cooling. Preferably, holding at a temperature of 30 to 70 ° C. promotes crystallization and improves the blocking resistance of the toner.

<Washing process>
Impurities in the resin particles can be removed by repeating washing and filtration of 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. By repeating washing with pure water and filtration a plurality of times, metal salts and surfactants in the resin particles can be removed. 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 can be dried to obtain toner particles.
The toner particles may be used as toner as they are. 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 to the toner particles by applying shear force in a dry state, Toner may be obtained. These inorganic fine particles and resin fine particles function as external additives such as fluidity aids and cleaning aids.

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

<Production of resin fine particle A1 dispersion>
-300 parts of toluene (made by Wako Pure Chemical Industries)-Ethylene-vinyl acetate copolymer EVA-A (R ₁ = H, R ₂ = H, R ₃ = CH ₃ , monomer unit Y2 content: 15% by mass, acid Value = 0 mg KOH / g, weight average molecular weight: 110000, softening point (Tm): 128 ° C., melting point: 86 ° C., elongation at break = 700%, (l + m + n) /W=1.00) 100 parts ・ olefinic acid group Containing copolymer A (ethylene-methacrylic acid copolymer EMA-A, melt flow rate: 60 g / 10 min, melting point = 90 ° C., acid value = 90 mg KOH / g) 25 parts or more are mixed at 90 ° C. Dissolved.
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 the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle A1 dispersion) having a resin fine particle A1 concentration of 20%.
The volume-based median diameter of the resin fine particles A1 was measured by using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.40 μm.

<Production of resin fine particle A2 dispersion>
EVA-A use amount 100 parts EVA-A 50 parts, ethylene-vinyl acetate copolymer EVA-B (R ₁ = H, R ₂ = H, R ₃ = CH ₃ , monomer unit Y2 content: 15 mass %, Acid value = 0 mg KOH / g, Tm: 83 ° C., melting point: 77 ° C., (l + m + n) /W=1.00) A fine particle A2 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A2 was 0.33 μm. The elongational viscosity in a state where EVA-A and EVA-B were mixed in equal amounts was 450%.

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

<Production of resin fine particle A4 dispersion>
EVA-A was changed to ethylene-ethyl acrylate copolymer EEA-A (R ₁ = H, R ₄ = H, R ₅ = C ₂ H ₅ , monomer unit Y2 content: 15% by mass, acid value = 0 mgKOH). / G, Tm: 125 ° C., melting point: 87 ° C., elongation at break = 800%, (l + m + n) /W=1.00) An A4 dispersion was obtained. The volume-based median diameter of the obtained resin fine particles was 0.54 μm.

<Production of resin fine particle A5 dispersion>
100 parts of EVA-A used is 80 parts of EVA-A, polyester resin PES-A [composition (molar ratio) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: isophthalate 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, Tm: 120 ° C., glass A resin fine particle A5 dispersion was obtained in the same manner as the production method of the resin fine particle A1 dispersion except that the transition temperature (Tg) = 70 ° C. and the acid value = 13 mgKOH / g] was changed to 20 parts. The volume-based median diameter of the obtained resin fine particles A5 was 0.33 μm.

<Production of resin fine particle A6 dispersion>
EVA-A is an 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, vinyl valerate Derived monomer unit (formula (4)) ratio: 4% by mass, acid value = 0 mgKOH / g, weight average molecular weight: 120,000, Tm: 130 ° C., melting point: 75 ° C., elongation at break = 600%, (l + m + n) / A resin fine particle A6 dispersion was obtained in the same manner as in the production method of the resin fine particle A1 dispersion, except that W = 0.96). The volume-based median diameter of the obtained resin fine particles A6 was 0.44 μm.

<Production of resin fine particle A7 dispersion>
EVA-A was converted to 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, vinyl valerate Derived monomer unit (formula (4)) ratio: 25% by mass, acid value = 0 mgKOH / g, weight average molecular weight: 110000, Tm: 118 ° C., melting point: 71 ° C., elongation at break = 550%, (l + m + n) / A resin fine particle A7 dispersion was obtained in the same manner as in the production method of the resin fine particle A1 dispersion, except that W = 0.75). The volume-based median diameter of the obtained resin fine particles A7 was 0.42 μm.

<Production 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 mgKOH / g, melting point : 105 ° C., Tm: 156 ° C., elongation at break = 600%, (l + m + n) /W=1.00) Obtained. The volume-based median diameter of the obtained resin fine particles A8 was 0.51 μm.

<Production 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 mgKOH / g, Tm The resin fine particle A9 dispersion was prepared in the same manner as the resin fine particle A1 dispersion except that the melting point was 160 ° C., the melting point was 40 ° C., the elongation at break = 870%, and (l + m + n) /W=1.00 Obtained. The volume-based median diameter of the obtained resin fine particles A9 was 0.51 μm.

<Production of resin fine particle A10 dispersion>
Olefinic acid group-containing copolymer A was converted to olefinic acid group-containing copolymer B (ethylene-methacrylic acid copolymer EMA-B, melt flow rate: 500 g / 10 min, melting point = 95 ° C., acid value = 60 mgKOH / A resin fine particle A10 dispersion was obtained in the same manner as in the method for producing the resin fine particle A2 dispersion, except that the method was changed to g). The volume-based median diameter of the obtained resin fine particles A10 was 0.42 μm.

<Production of resin fine particle A11 dispersion>
Olefinic acid group-containing copolymer A was converted to olefinic acid group-containing copolymer C (ethylene-methacrylic acid copolymer EMA-C, melt flow rate: 60 g / 10 min, melting point = 87 ° C., acid value = 120 mgKOH / A resin fine particle A11 dispersion was obtained in the same manner as in the production method of the resin fine particle A2 dispersion except that the method was changed to g). The volume-based median diameter of the obtained resin fine particles A11 was 0.39 μm.

<Production of resin fine particle A12 dispersion>
Olefinic acid group-containing copolymer A was converted to olefinic acid group-containing copolymer D (ethylene-methacrylic acid copolymer EMA-D, melt flow rate: 130 g / 10 min, melting point = 90 ° C.,
A resin fine particle A12 dispersion was obtained in the same manner as in the production method of the resin fine particle A2 dispersion except that the acid value was changed to 12 mgKOH / g). The volume-based median diameter of the obtained resin fine particles A12 was 0.52 μm.

<Production of resin fine particle A13 dispersion>
Without using EVA-A and olefinic acid group-containing copolymer A, polyester resin 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, Tm: 120 A resin fine particle A13 dispersion was obtained in the same manner as the resin fine particle A1 dispersion, except that 125 parts of [° C., glass transition temperature (Tg) = 70 ° C., acid value = 13 mgKOH / g] were used. The volume-based median diameter of the obtained resin fine particles A13 was 0.25 μm.

<Production of resin fine particle A14 dispersion>
Polyester resin PES-A was converted to crystalline polyester resin 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) In the same manner as in the production method of resin fine particle A13 dispersion, resin fine particle A14 A dispersion was obtained. The volume-based median diameter of the obtained resin fine particles A14 was 0.25 μm.

<Production of cross-linking agent A>
A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 470 parts of isopropyl alcohol and heated to 80 ° C. while gently flowing nitrogen gas. A monomer mixture consisting of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline and 84 parts of methoxypolyethylene glycol acrylate prepared in advance, and ABN-E (manufactured by Nippon Hydrazine Kogyo Co., Ltd.) Polymerization initiator: An initiator solution consisting of 21 parts of 2,2′-azobis (2-methylbutyronitrile) and 189 parts of isopropyl alcohol was added dropwise over 2 hours using a dropping funnel. During the reaction, nitrogen gas was kept flowing, and the temperature in the flask was kept at 80 ± 1 ° C. Even after completion of the dropwise addition, the mixture was kept at the same temperature for 5 hours and then cooled to obtain an oxazoline group-containing polymer A (crosslinking agent A). The obtained crosslinking agent A had an oxazoline value of 220 g-solid / eq. Met.

<Production of cross-linking agent B>
A crosslinking agent B was obtained in the same manner as the crosslinking agent A except that 63 parts of methyl methacrylate, 315 parts of 2-isopropenyl-2-oxazoline and 42 parts of methoxypolyethylene glycol acrylate were used. The obtained crosslinking agent B had an oxazoline value of 145 g-solid / eq. Met.

<Production of cross-linking agent C>
A crosslinking agent C was obtained in the same manner as the crosslinking agent A except that 189 parts of methyl methacrylate, 105 parts of 2-isopropenyl-2-oxazoline, and 126 parts of methoxypolyethylene glycol acrylate were used. The obtained crosslinking agent C had an oxazoline value of 440 g-solid / eq. Met.

<Production of cross-linked resin fine particle B1 dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries) 300 parts-Ethylene-vinyl acetate copolymer EVA-A 100 parts-Crosslinking agent A 5 parts-Olefinic acid group-containing copolymer EMA-A 20 parts It was 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 the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, the fine particle aqueous dispersion obtained by removing toluene using an evaporator is heated at 90 ° C. for 3 hours, and the concentration is adjusted with ion-exchanged water. A liquid (crosslinked resin fine particle B1 dispersion) was obtained.
The volume-based median diameter of the crosslinked resin fine particles B1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.45 μm.

<Manufacture of crosslinked resin fine particles B2>
The cross-linked resin fine particle B2 dispersion is the same as the production method of the cross-linked resin fine particle B1 dispersion except that 100 parts of EVA-A is changed to 50 parts of EVA-A and 50 parts of ethylene-vinyl acetate copolymer EVA-B. Got. The volume-based median diameter of the obtained crosslinked resin fine particles B2 was 0.32 μm.

<Production of cross-linked resin fine particle B3 dispersion>
A crosslinked resin fine particle B3 dispersion was obtained in the same manner as the crosslinked resin fine particle B2 dispersion except that the crosslinking agent A was changed to the crosslinking agent B. The volume-based median diameter of the obtained crosslinked resin fine particles B3 was 0.36 μm.

<Production of Crosslinked Resin Fine Particle B4 Dispersion>
A crosslinked resin fine particle B4 dispersion was obtained in the same manner as the crosslinked resin fine particle B2 dispersion except that the crosslinking agent A was changed to the crosslinking agent C. The volume-based median diameter of the obtained crosslinked resin fine particles B4 was 0.38 μm.

<Production of cross-linked resin fine particle B5 dispersion>
-Toluene (made by Wako Pure Chemical Industries) 300 parts-Ethylene-vinyl acetate copolymer EVA-A 50 parts-Ethylene-vinyl acetate copolymer EVA-B 50 parts-Olefinic acid group-containing copolymer A 20 parts or more The 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 the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator to obtain a fine particle aqueous dispersion.
The resulting fine particle aqueous dispersion was mixed with a crosslinking agent D (product name: Carbodilite V-02-L2, manufactured by Nisshinbo, carbodiimide value (polymer weight per 1 mol of carbodiimide group) 385 g-solid / eq. 40 mass% aqueous solution). After adding 5 parts, the mixture was heated at 90 ° C. for 3 hours, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (crosslinked resin fine particle B5 dispersion) having a resin fine particle B5 concentration of 20%. The volume-based median diameter of the crosslinked resin fine particles B5 was 0.32 μm.

<Production of cross-linked resin fine particle B6 dispersion>
The same as the dispersion resin fine particle B5 dispersion except that 12.5 parts of the crosslinking agent D was changed to 20 parts of crosslinking agent E (product name: Epocross WS-700, manufactured by Nippon Shokubai Co., Ltd., oxazoline value 220 g-solid / eq. 25 mass% aqueous solution). Thus, a crosslinked resin fine particle B6 dispersion was obtained. The volume-based median diameter of the obtained crosslinked resin fine particles B6 was 0.33 μm.

<Production of cross-linked resin fine particle B7 dispersion>
The same as the cross-linked resin fine particle B5 dispersion, except that 12.5 parts of the cross-linking agent D was changed to 50 parts of cross-linking agent F (product name: Epocross WS-300, manufactured by Nippon Shokubai Co., Ltd., oxazoline value 130 g-solid / eq. 10 mass% aqueous solution). A crosslinked resin fine particle B7 dispersion was obtained. The volume-based median diameter of the obtained crosslinked resin fine particles B7 was 0.36 μm.

<Manufacture of crosslinked resin fine particles B8>
A crosslinked resin fine particle B8 dispersion was obtained in the same manner as the production method of the crosslinked resin fine particle B1 dispersion except that EVA-A was changed to ethylene-ethyl acrylate copolymer EEA-A. The volume-based median diameter of the obtained crosslinked resin fine particles B8 was 0.55 μm.

<Production of crosslinked resin fine particles B9>
A crosslinked resin fine particle B9 dispersion was obtained in the same manner as the production method of the crosslinked resin fine particle B1 dispersion except that 100 parts of EVA-A was changed to 75 parts of EVA-A and 25 parts of polyester resin PES-A. The volume-based median diameter of the obtained crosslinked resin fine particles B9 was 0.52 μm.

<Production of crosslinked resin fine particles B10>
A crosslinked resin fine particle B10 dispersion was obtained in the same manner as the production method of the crosslinked resin fine particle B1 dispersion except that EVA-A was changed to EVA-C. The volume-based median diameter of the obtained crosslinked resin fine particles B10 was 0.46 μm.

<Production of crosslinked resin fine particles B11>
A crosslinked resin fine particle B11 dispersion was obtained in the same manner as the production method of the crosslinked resin fine particle B1 dispersion except that EVA-A was changed to EVA-D. The volume-based median diameter of the obtained crosslinked resin fine particles B11 was 0.40 μm.

<Production of cross-linked resin fine particle B12 dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries) 300 parts-Olefinic acid group-containing copolymer A 100 parts-Crosslinking agent A 25 parts The above formulations were mixed and dissolved at 90 ° C.
Separately, 0.7 parts of sodium dodecylbenzenesulfonate, 1.5 parts of sodium laurate, and 2.0 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 the aqueous solution were mixed, and the ultra-high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, the fine particle aqueous dispersion obtained by removing toluene using an evaporator is heated at 90 ° C. for 3 hours, the concentration is adjusted with ion-exchanged water, and the aqueous fine dispersion of resin fine particle B12 is 20% in concentration. A liquid (crosslinked resin fine particle B12 dispersion) was obtained.
The volume-based median diameter of the crosslinked resin fine particles B1 was 0.89 μm.

<Production of crosslinked resin fine particles B13>
A crosslinked resin fine particle B13 dispersion was obtained in the same manner as the method for producing the crosslinked resin fine particle B2 dispersion, except that EMA-A was changed to EMA-B. The volume-based median diameter of the obtained crosslinked resin fine particles B13 was 0.46 μm.
<Production of crosslinked resin fine particles B14>
A crosslinked resin fine particle B14 dispersion was obtained in the same manner as the method for producing the crosslinked resin fine particle B2 dispersion, except that EMA-A was changed to EMA-C. The volume-based median diameter of the obtained crosslinked resin fine particles B14 was 0.42 μm.

<Manufacture of crosslinked resin fine particles B15>
A crosslinked resin fine particle B15 dispersion was obtained in the same manner as the production method 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 crosslinked resin fine particles B15 was 0.56 μm.
<Production of crosslinked resin fine particles B16>
A crosslinked resin fine particle B16 dispersion was obtained in the same manner as the production method 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 crosslinked resin fine particles B16 was 0.42 μm.

<Manufacture of crosslinked resin fine particles B17>
A crosslinked resin fine particle B17 dispersion was obtained in the same manner as the method for producing the crosslinked resin fine particle B2 dispersion except that EMA-A was changed to EMA-D. The volume-based median diameter of the obtained crosslinked resin fine particles B17 was 0.59 μm.
<Manufacture of crosslinked resin fine particles B18>
A crosslinked resin fine particle B18 dispersion was obtained in the same manner as the production method of the crosslinked resin fine particle B1 dispersion except that EVA-A was changed to the polyester resin PES-A. The volume-based median diameter of the obtained crosslinked resin fine particles B18 was 0.33 μm.

<Manufacture of silicone oil emulsion>
・ Silicone oil 20.0 parts (Dimethyl silicone oil, Shin-Etsu Chemical Co., Ltd .: KF96-50CS)
・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part ・ Ion-exchanged water 79.0 parts Mix and dissolve the above, and use high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). An aqueous dispersion with 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.

<Manufacture 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 the 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.

<Manufacture of aliphatic hydrocarbon compound fine particle dispersion>
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., Nippon Seiwa) 20.0 parts Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.0 part Ion-exchanged water 79. After putting 0 parts or more into a mixing vessel equipped with a stirrer, the mixture was 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 system is cooled to 40 ° C. under the cooling treatment conditions of a rotor rotational speed of 1000 r / min, a screen rotational speed of 0 r / min, and a cooling rate of 10 ° C./min. A dispersion (aliphatic hydrocarbon compound fine particle dispersion) was obtained. The volume-based median diameter of the aliphatic hydrocarbon compound fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

<Example 1: Production of toner 1>
-Resin fine particle A1 dispersion 450 parts-Crosslinked resin fine particle B1 dispersion 50 parts-Colorant fine particle dispersion 80 parts-Aliphatic hydrocarbon compound fine particle dispersion 150 parts-Silicone oil emulsion 100 parts-Ion exchange water 110 parts Above 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, the volume average particle diameter of the formed aggregate particles was measured using Coulter Multisizer III. It was confirmed that aggregate particles having a volume average particle diameter of about 6.0 μm were formed.
After adding 340 parts of 5% ethylenediamine tetraacetate aqueous solution to the dispersion of 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 degree | times and filtering and solid-liquid separation, the filtrate was wash | cleaned with 0.5% ethylenediamine tetraacetate aqueous solution, and also wash | cleaned with ion-exchange water. The toner particles having a volume-based median diameter of 5.2 μm were obtained by drying using a vacuum dryer after washing.
To 100 parts of the obtained toner particles, 1.5 parts of hydrophobic silica fine powder having a primary particle diameter of 10 nm and 2.5 parts of hydrophobic silica fine powder having a primary particle diameter of 100 nm were added. Toner 1 was obtained by dry mixing with a Henschel mixer (Mitsui Mine). The constituent conditions of the obtained toner 1 are shown in Tables 1-3.

<Example 2>
Toner 2 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A2 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B2. The volume-based median diameter of the toner particles was 5.2 μm.
<Example 3>
Toner 3 was obtained in the same manner as in Example 2 except that the amount of resin fine particle A2 dispersion used was 350 parts and the amount of crosslinked resin fine particle B2 dispersion used was 150 parts. The volume-based median diameter of the toner particles was 5.6 μm.
<Example 4>
Toner 4 was obtained in the same manner as in Example 2, except that the amount of resin fine particle A2 dispersion used was 300 parts and the amount of crosslinked resin fine particle B2 dispersion used was 200 parts. The volume-based median diameter of the toner particles was 5.5 μm.

<Example 5>
A toner 5 was obtained in the same manner as in Example 2 except that the amount of the resin fine particle A2 dispersion used was 480 parts and the amount of the crosslinked resin fine particle B2 dispersion used was 20 parts. The volume-based median diameter of the toner particles was 5.1 μm.
<Example 6>
Toner 6 was obtained in the same manner as in Example 2 except that the aliphatic hydrocarbon compound fine particle dispersion was not used. The volume-based median diameter of the toner particles was 5.5 μm.
<Example 7>
A toner 7 was obtained in the same manner as in Example 2 except that the crosslinked resin fine particles B2 were changed to the crosslinked resin fine particles B3. The volume-based median diameter of the toner particles was 5.4 μm.

<Example 8>
A toner 8 was obtained in the same manner as in Example 2 except that the crosslinked resin fine particles B2 were changed to the crosslinked resin fine particles B4. The volume-based median diameter of the toner particles was 5.4 μm.
<Example 9>
A toner 9 was obtained in the same manner as in Example 2 except that the crosslinked resin fine particles B2 were changed to the crosslinked resin fine particles B5. The volume-based median diameter of the toner particles was 5.0 μm.
<Example 10>
A toner 10 was obtained in the same manner as in Example 2 except that the crosslinked resin fine particles B2 were changed to the crosslinked resin fine particles B6. The volume-based median diameter of the toner particles was 5.3 μm.

<Example 11>
A toner 11 was obtained in the same manner as in Example 2 except that the crosslinked resin fine particles B2 were changed to the crosslinked resin fine particles B7. The volume-based median diameter of the toner particles was 5.1 μm.
<Example 12>
A toner 12 was obtained in the same manner as in Example 2 except that the resin fine particles A2 were changed to the resin fine particles A3. The volume-based median diameter of the toner particles was 5.2 μm.
<Example 13>
Toner 13 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A4 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B8. The volume-based median diameter of the toner particles was 5.6 μm.

<Example 14>
A toner 14 was obtained in the same manner as in Example 1 except that the resin fine particles A1 were changed to resin fine particles A5 and the crosslinked resin fine particles B1 were changed to crosslinked resin fine particles B9. The volume-based median diameter of the toner particles was 5.5 μm.
<Example 15>
A toner 15 was obtained in the same manner as in Example 1 except that the resin fine particles A1 were changed to resin fine particles A6 and the crosslinked resin fine particles B1 were changed to crosslinked resin fine particles B10. The volume-based median diameter of the toner particles was 5.4 μm.
<Example 16>
Toner 16 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A7 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B11. The volume-based median diameter of the toner particles was 5.3 μm.

<Example 17>
Toner 17 was obtained in the same manner as in Example 2, except that the amount of resin fine particle A2 dispersion used was 490 parts, and 10 parts of crosslinked resin fine particle B12 dispersion was used instead of the crosslinked resin fine particle B2 dispersion. The volume-based median diameter of the toner particles was 5.8 μm.
<Example 18>
A toner 18 was obtained in the same manner as in Example 2 except that the amount of the silicone oil emulsion used was 150 parts. The volume-based median diameter of the toner particles was 5.2 μm.

<Example 19>
A toner 19 was obtained in the same manner as in Example 1 except that the resin fine particles A1 were changed to resin fine particles A10 and the crosslinked resin fine particles B1 were changed to crosslinked resin fine particles B13. The volume-based median diameter of the toner particles was 5.5 μm.
<Example 20>
Toner 20 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A11 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B14. The volume-based median diameter of the toner particles was 5.3 μm.

<Comparative Example 1>
Comparative toner 1 was obtained in the same manner as in Example 12 except that the amount of the resin fine particle A3 dispersion used was 500 parts and the crosslinked resin fine particle B2 was not used. The volume-based median diameter of the toner particles was 7.6 μm.
<Comparative example 2>
A comparative toner 2 was obtained in the same manner as in Example 1 except that the resin fine particles A1 were changed to resin fine particles A8 and the crosslinked resin fine particles B1 were changed to crosslinked resin fine particles B15. The volume-based median diameter of the toner particles was 6.0 μm.

<Comparative Example 3>
Comparative toner 3 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A9 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B16. The volume-based median diameter of the toner particles was 5.3 μm.
<Comparative Example 4>
Comparative toner 4 was obtained in the same manner as in Example 1 except that resin fine particle A1 was changed to resin fine particle A12 and cross-linked resin fine particle B1 was changed to cross-linked resin fine particle B17. The volume-based median diameter of the toner particles was 5.0 μm.
<Comparative Example 5>
Comparative toner 5 was obtained in the same manner as in Example 2 except that the silicone oil emulsion was not used. The volume-based median diameter of the toner particles was 5.2 μm.

<Comparative Example 6>
-Resin fine particle A13 dispersion 450 parts-Crosslinked resin fine particle B18 dispersion 50 parts-Colorant fine particle dispersion 80 parts-Aliphatic hydrocarbon compound fine particle dispersion 50 parts-Ion exchange water 310 parts After putting into a flask and mixing, 60 parts of 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 60 ° C. for 20 minutes, the volume average particle diameter of the formed aggregate particles was measured using Coulter Multisizer III. It was confirmed that aggregate particles having a volume average particle diameter of about 6.0 μm were formed.
After adding 340 parts of 5% ethylenediamine tetraacetate aqueous solution to the dispersion of 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 25 degree | times, after washing | cleaning with ion-exchange water after filtering and solid-liquid separation. The toner particles having a volume-based median diameter of 5.8 μm were obtained by drying using a vacuum dryer after washing.
To 100 parts of the obtained toner particles, 1.5 parts of hydrophobic silica fine powder having a primary particle diameter of 10 nm and 2.5 parts of hydrophobic silica fine powder having a primary particle diameter of 100 nm were added. Comparative toner 6 was obtained by dry mixing with a Henschel mixer (Mitsui Mine).

<Comparative Example 7>
A comparative toner 7 was obtained in the same manner as in Comparative Example 6 except that the resin fine particles A13 were changed to resin fine particles A14 and the crosslinked resin fine particles B18 were not used. The volume-based median diameter of the toner particles was 5.8 μm.

The following evaluation tests were performed using the toners. The evaluation results are shown in Table 4.
<Evaluation of storage stability (blocking resistance)>
The toner was allowed to stand for 3 days in a thermostatic chamber at 50 ° C. and a humidity of 50%, and the degree of blocking was visually evaluated.
A: No blocking occurs, or even if blocking occurs, it is easily dispersed by light vibration.
B: Blocking occurs, but disperses when it continues to vibrate.
C: Blocking occurs and does not disperse even when force is applied.

<Evaluation of storage stability during long-term storage>
The toner was allowed to stand for 60 days in a constant temperature and humidity chamber under the conditions of 40 ° C. and humidity 80%, and the degree of blocking was visually evaluated.
A: No blocking occurs, or even if blocking occurs, it is easily dispersed by light vibration.
B: Blocking occurs, but disperses when it continues to vibrate.
C: Blocking occurs and does not disperse even when force is applied.

<Evaluation of low-temperature fixability>
The toner and a ferrite carrier surface-coated with a silicone resin (average particle size 42 μm) were mixed so that the toner concentration was 8% by mass to prepare a two-component developer. A commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) was used to form an unfixed toner image (0.75 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 remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. The condition when the unfixed image was fixed was evaluated visually by setting the process speed to 357 mm / sec under a room temperature of 15 ° C. and a humidity of 10%.
A: Fixing is possible at a temperature of 140 ° C. or lower.
B: Fixing is possible at a temperature higher than 140 ° C. and lower than 150 ° C.
C: Fixing is possible at a temperature higher than 150 ° C. and not higher than 200 ° C., or there is no temperature range where fixing is possible.

<Evaluation of eraser resistance>
The toner was fixed by the same method as the low temperature fixability evaluation method, and the fixed product at 155 ° C. was tested for erasure resistance using an eraser (product name: MONO, manufactured by Dragonfly Pencil Co., Ltd.).
A: Not erased with an eraser.
B: Image density decreases when rubbed with eraser.
C: Erased with an eraser.

<Evaluation of charge retention>
0.01 g of toner was weighed into an aluminum pan and charged to −600 V using a corona charging device (KTB-20, manufactured by Kasuga Electric). Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface potentiometer (model 347 manufactured by Trek Japan) in an atmosphere of 30 ° C. and 80% humidity. From the measurement results, the charge retention was calculated from the following equation.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) × 100
A: Charge retention is 90% or more.
B: The charge retention is 50% or more and less than 90%.
C: The charge retention is 10% or more and less than 50%.
D: Charge retention is less than 10%.

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

<Evaluation of hot offset resistance>
The toner and a ferrite carrier surface-coated with a silicone resin (average particle size 42 μm) were mixed so that the toner concentration was 8% by mass to prepare a two-component developer. A commercially available full color digital copying machine (CLC1100, manufactured by Canon Inc.) was used to form an unfixed toner image (0.1 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 remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. The condition when the unfixed image was fixed was evaluated visually by setting the process speed to 357 mm / sec under a room temperature of 23 ° C. and a humidity of 5%.
A: Hot offset occurs at a temperature of 160 ° C. or higher, 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: Hot offset occurs at a temperature higher than 130 ° C and lower than 140 ° C.
D: Hot offset occurs at a temperature of 130 ° C. or lower.

Claims (12)

A toner comprising toner particles containing a resin component and silicone oil,
The resin component is
A modified polyolefin crosslinked product which is a reaction product of an olefinic acid group-containing copolymer having a carboxy group and a crosslinking agent having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less;
An olefinic ester group-containing copolymer;
Have
The olefin-based ester group-containing copolymer is
Monomer unit Y1 represented by the following formula (1);
At least one monomer unit Y2 selected from the group of monomer units represented by the following formula (2) and monomer units represented by the following formula (3);
Have
The content of the olefinic ester group-containing copolymer in the resin component is 50% by mass or more based on the total mass of the resin component,
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 olefinic ester group-containing copolymer.
The toner, wherein the crosslinking agent has two or more groups selected from an oxazoline group and a carbodiimide group in the molecule.

(Wherein R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , R ⁴ represents H or CH ₃ , R ⁵ represents Represents CH ₃ or C ₂ H _5. ) The total mass of the olefin ester group-containing copolymer is W, and the mass of the monomer unit represented by the formula (1), the monomer unit represented by the formula (2), and the monomer unit represented by the formula (3). Are l, m, and n, respectively.
The toner according to claim 1, wherein a value of (l + m + n) / W is 0.80 or more.   The toner according to claim 1, wherein the content of the modified polyolefin crosslinked body is 1% by mass or more and 8% by mass or less based on the total mass of the resin component. The crosslinking agent is a polymer containing an oxazoline group,
The toner according to claim 1, wherein the cross-linking agent has an oxazoline value of 150 g-solid / eq or more and 400 g-solid / eq or less.   The toner according to claim 1, wherein a content of the silicone oil is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin component.   The toner according to any one of claims 1 to 5, wherein the resin component contains an olefinic acid group-containing copolymer having a carboxy group having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less. Two or more types of the olefin ester group-containing copolymer are contained,
The softening point in the flow tester measurement of at least one copolymer is 120 ° C or higher and 160 ° C or lower, and the softening point in the at least one flow tester measurement is 70 ° C or higher and 100 ° C or lower. The toner according to item. 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 the 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 according to claim 1, wherein the olefinic ester group-containing copolymer contains an ethylene-vinyl acetate copolymer. A method for producing a toner comprising toner particles containing a resin component and silicone oil,
Including a preparation step of preparing a resin fine particle dispersion in which the resin fine particles for generating the resin component are dispersed in an aqueous medium,
The resin component is
A modified polyolefin crosslinked product which is a reaction product of an olefinic acid group-containing copolymer having a carboxy group and a crosslinking agent having an acid value of 50 mgKOH / g or more and 300 mgKOH / g or less;
An olefinic ester group-containing copolymer;
Have
The olefin-based ester group-containing copolymer is
Monomer unit Y1 represented by the following formula (1);
At least one monomer unit Y2 selected from the group of monomer units represented by the following formula (2) and monomer units represented by the following formula (3);
Have
The content of the olefinic ester group-containing copolymer in the resin component is 50% by mass or more based on the total mass of the resin component,
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 olefinic ester group-containing copolymer.
A method for producing a toner, wherein the crosslinking agent has two or more groups selected from an oxazoline group and a carbodiimide group in the molecule.

(Wherein R ¹ represents H or CH ₃ , R ² represents H or CH ₃ , R ³ represents CH ₃ or C ₂ H ₅ , R ⁴ represents H or CH ₃ , R ⁵ represents 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
Further comprising a fusing step of fusing the aggregate particles by heating.
The method for producing a toner according to claim 10. The olefin ester group-containing copolymer contains an ethylene-vinyl acetate copolymer,
The olefinic acid group-containing copolymer contains an ethylene methacrylic acid copolymer or an ethylene acrylic acid copolymer,
The crosslinking agent is a polymer containing an oxazoline group,
The method for producing a toner according to claim 10, wherein the cross-linking agent has an oxazoline value of 150 g-solid / eq or more and 400 g-solid / eq or less.