JP2020187270A - toner - Google Patents

Abstract

To provide a toner that is excellent in low-temperature fixability and separability during fixing, reduces the likelihood of the occurrence of attachment of a mold release agent to a member included in an image forming device, and can obtain an image excellent in rubbing resistance.SOLUTION: The present invention relates to a toner for electrostatic latent image development having toner particles each containing a binder resin and a mold release agent. The binder resin contains a crystalline polyester resin. The mold release agent contains ester wax and hydrocarbon wax. In an absorption spectrum obtained by leaving the toner standing under an environment of 100°C for 60 minutes and then measuring by the total reflection method with the use of an infrared spectrophotometer, the toner has a maximum absorption peak within an absorption wave number range of 2900 cm-1 or more and 2930 cm-1 or less, and the peak intensity P1 of the absorption maximum peak satisfies the following formula (1). (1) 0.02≤P1≤0.06.SELECTED DRAWING: Figure 1

Description

The present invention relates to toner.

In recent years, there has been an increasing demand for energy saving in electrophotographic image forming apparatus and the like from the viewpoint of reducing the environmental load, and the development of toner that can be fixed with less energy is being promoted.

As a typical method for lowering the fixing temperature of toner, a method of using a crystalline resin as a fixing resin is known. The crystalline resin melts rapidly at the melting point, and the amorphous resin is plasticized to achieve low temperature fixability.

In addition, the toner contains a mold release agent. The release agent exudes from the toner matrix particles when the toner image is fixed, enhances the fixing separability between the fixing member and the toner image at the time of fixing, and enhances the abrasion resistance of the fixed image. Patent Document 1 and Patent Document 2 describe toners containing two types of mold release agents.

In Patent Document 1, in a toner for forming an electrostatic charge image containing a styrene- (meth) -acrylic copolymer resin as a binder resin, two or more kinds of paraffin waxes having different melting temperatures are contained as a release agent. In addition, a toner in which most of the mold release agent is contained in the surface layer side region of the toner is described. According to Patent Document 1, the content of the release agent is reduced by using a styrene- (meth) -acrylic copolymer resin as the binder resin and containing a large amount of the release agent in the surface layer side region of the toner. However, it is stated that the amount of exudation of the release agent can be made sufficient. Further, in Patent Document 1, in the above two or more kinds of paraffin wax, the release agent is quickly recrystallized after the paraffin wax on the high dissolution temperature side is fixed, and after the paraffin wax on the low dissolution temperature side is fixed. It is stated that since the release agent is slowly recrystallized, the crystallization rate is constant regardless of the temperature history, and fluctuations in the amount of release agent seepage are suppressed.

Further, Patent Document 2 describes a plurality of toners for forming an electrostatic charge image containing a crystalline resin as a binder resin, which contain at least two types of mold release agents and are observed at the time of temperature decrease in differential scanning calorimetry. Toners are described in which the peak tops of the exothermic peaks are all 80 ° C. or lower. In Patent Document 2, the release having a melting point closer to the melting point of the crystalline resin is obtained by containing at least two kinds of mold release agents in the toner and forming separate crystal domains in the mold release agent and the crystalline resin. It is described that the mold release function of the mold agent is further enhanced, and the mold release agent can be easily dissolved and the mold release agent can be easily exuded.

Japanese Unexamined Patent Publication No. 2015-184574 JP-A-2017-223854

As described in Patent Document 1 and Patent Document 2, toners containing two types of mold release agents are known. However, the toners described in Patent Document 1 and Patent Document 2 also have a demand for further improving the fixing separability and the abrasion resistance, which are the original actions of the release agent.

If the release agent exuded from the toner cannot be sufficiently crystallized during image formation, the uncrystallized release agent adheres to the member of the image forming apparatus during the paper ejection process and is further ejected later. It may reattach to the paper from the member and contaminate subsequent images.

The present invention has been made based on the above findings, and provides an image having excellent low-temperature fixability and fixing separability, less likely to cause the release agent to adhere to a member of an image forming apparatus, and excellent scratch resistance. Its purpose is to provide a toner that can be obtained.

The above problem is solved by a toner for electrostatic latent image development having toner particles containing a binder resin and a mold release agent. In the toner, the binder resin contains a crystalline polyester resin, the mold release agent contains an ester wax and a hydrocarbon wax, and the toner is red after being allowed to stand in an environment of 100 ° C. for 60 minutes. In the absorption spectrum measured by the total reflection method using an external spectrophotometer, the absorption maximum peak is in the range where the absorption wavenumber is 2900 cm ^-1 or more and 2930 cm ^-1 or less, and the peak intensity P1 of the absorption maximum peak is The following equation (1) is satisfied.
0.02 ≤ P1 ≤ 0.06 ... Equation (1)

INDUSTRIAL APPLICABILITY The present invention provides a toner that is excellent in low-temperature fixability and fixing separability, is less likely to cause the release agent to adhere to a member of an image forming apparatus, and can obtain an image having excellent scratch resistance.

FIG. 1 is a schematic view showing an example of an image forming apparatus capable of preferably using the toner of the present invention.

Hereinafter, an embodiment of the present invention will be described in detail.

[Toner configuration]
The toner (toner for electrostatic latent image development) may be a one-component developer or a two-component developer. The toner of a one-component developer is composed of toner particles. Further, the toner of the two-component developer is composed of toner particles and carrier particles. In the present embodiment, the toner particles include toner matrix particles containing a binder resin and a mold release agent, and an external additive.

Examples of carrier particles include magnetic particles made of metals such as iron, ferrite and magnetite, and conventionally known materials such as alloys of these metals with metals such as aluminum and lead. The carrier particles may be coated carrier particles having a core material particle made of a magnetic material and a coating material layer covering the surface thereof, or a resin in which fine powder of the magnetic material is dispersed in a resin. It may be a dispersed carrier particle. As the carrier particles, coated carrier particles are preferable from the viewpoint of suppressing adhesion of the carrier particles to the photoconductor.

The average particle size of the carrier particles is preferably 20 μm or more and 100 μm or less, and more preferably 25 μm or more and 80 μm or less in terms of volume-based median diameter. The volume-based median diameter of the carrier particles can be measured by, for example, a laser diffraction type particle size distribution measuring device (HELOS; SYMPATEC) equipped with a wet disperser.

The mixing ratio (mass ratio) of the toner particles and the carrier particles is not particularly limited, but from the viewpoint of chargeability and storage stability, the toner particles: carrier particles = 1: 100 to 30: 100 is preferable. More preferably, it is 100 to 20: 100.

The toner particles include, for example, the toner matrix particles and an external additive present on the surface thereof.

[Toner matrix particles]
The toner base particles are particles containing a binder resin and various additives including a mold release agent.

In the toner base particles, the binder resin contains crystalline polyester, and the release agent contains ester wax and hydrocarbon wax. The toner containing the toner matrix particles has an absorption wave number of 2900 cm- ¹ or more and 2930 cm in the absorption spectrum measured by the total reflection method using an infrared spectrophotometer after being allowed to stand in an environment of 100 ° C. for 60 minutes. ^It has an absorption maximum peak in the range of ^-1 or less, and the peak intensity P1 of the absorption maximum peak satisfies the following formula (1).
0.02 ≤ P1 ≤ 0.06 ... Equation (1)

Since the binder resin contains crystalline polyester, the toner base particles have a lower melt viscosity and a lower viscosity at the time of melting. Therefore, it is considered that the toner base particles are likely to be sufficiently exuded by the release agent at the time of fixing, are excellent in low temperature fixability and fixing separability, and are easy to obtain an image having excellent abrasion resistance. Further, in the above two types of mold release agents, since the mold release agent having a lower melting point easily exudes from the toner at the time of fixing, it is considered that the fixing separability is improved and it is easy to obtain an image having excellent scratch resistance. In addition, since the above two types of release agents crystallize first after the release agent having a higher melting point exudes and become crystal nuclei that promote the crystallization of the release agent having a lower melting point, after exudation. It is considered that the crystallization of the mold is likely to proceed, and the adhesion of the uncrystallized mold release agent (hereinafter, also simply referred to as “release agent adhesion”) to the member of the image forming apparatus in the paper ejection process is unlikely to occur. ..

However, according to the findings of the present inventors, the toner matrix particles containing the two types of mold release agents cannot sufficiently exude from the toner matrix particles when the mold release agent having a higher melting point is fixed. Then, the release agent having a higher melting point stays inside the toner matrix particles and blocks the exudation path of the release agent from the inside of the toner matrix particles, thereby inhibiting the exudation of the release agent having a lower melting point. Resulting in. Therefore, it is considered that the amount of the release agent exuded from the toner matrix particles can be made more sufficient by eliminating the exudation suppressing effect.

Specifically, in the present embodiment, a crystalline polyester is used as the binder resin, and a larger amount of the release agent is distributed in the region on the surface layer side of the toner matrix particles, whereby the toner matrix at the time of fixing is used. Promotes the exudation of the release agent from the particles. With such a toner, after heating under conditions simulating the fixing time, the absorption spectrum measured by an infrared spectrophotometer shows the peak of CH reverse target expansion and contraction vibration derived from the release agent (2900 cm ^-1 to 2900 cm ^-1 to ¹ ). A maximum absorption peak is observed at 2930 cm ^-1 ). Then, since the release agent sufficiently exudes from the toner matrix particles, the peak intensity P1 of the absorption maximum peak becomes 0.02 or more.

On the other hand, the peak intensity P1 is set to 0.06 or less in order to suppress the occurrence of mold release agent adhesion due to an excessive amount of the release agent exuding from the toner matrix particles.

From the above viewpoint, the peak intensity P1 preferably satisfies the following formula (2).
0.03 ≤ P1 ≤ 0.05 ... Equation (2)

The peak intensity P1 is the ratio of the release agent present in the range from the outer edge of the toner matrix particles to a depth of 1/2 of the radius of the toner matrix particles (hereinafter, also simply referred to as “surface layer side distribution ratio”). Can be adjusted to be included in the above range by increasing. From the above viewpoint, the surface layer side distribution ratio is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. The upper limit of the distribution rate on the surface layer side is not particularly limited, but may be 100%.

The surface layer distribution ratio is from the outer edge of the toner matrix particles to a depth of 1/2 of the radius of the toner matrix particles with respect to the total area of the release agent in the cross section including the central axis of the toner matrix particles. It can be a percentage of the total area of the release agent present in the range. The area of the mold release agent in the above cross section is determined by image analysis of a reflected electron image obtained by imaging a cross section of a toner dyed with ruthenium tetroxide (RuO ₄ ) or the like with a scanning transmission electron microscope (STEM). Can be measured. Specifically, the domain in the toner particles can be discriminated by the difference in contrast stained with ruthenium tetroxide. Of the observed domains, the lighter-stained domain portion is observed as the release agent domain, and the darker-stained domain portion is observed as the binder resin domain.

In addition, the peak intensity P1 can also be adjusted by blending a release agent (melting points of ester wax and hydrocarbon wax, respectively, content and content ratio, etc.), blending of a binder resin, and the like.

(Bundling resin)
The binding resin contains a crystalline polyester resin.

The crystalline polyester resin is a crystalline polyester resin. Here, "crystallinity" means having a clear endothermic peak rather than a stepped endothermic change in differential scanning calorimetry (DSC). The "clear endothermic peak" specifically means a peak in which the half width of the endothermic peak is within 15 ° C. when measured at a heating rate of 10 ° C./min in DSC. The smaller the half width of the endothermic peak, the higher the crystallinity.

The crystalline polyester resin is preferable from the viewpoint of improving low-temperature fixability. The melting point of the crystalline polyester resin is preferably 50 ° C. or higher and 85 ° C. or lower from the viewpoint of sufficiently softening the toner to ensure sufficient low-temperature fixability, and further improving various properties in a well-balanced manner. , 60 ° C. or higher and 80 ° C. or lower is more preferable. The melting point of the crystalline polyester resin can be controlled by the resin composition (for example, the type of monomer). One type of the crystalline polyester resin may be used alone, or two or more types may be used in combination.

The crystalline polyester resin can be produced, for example, by a known synthetic method by a dehydration condensation reaction of a polyvalent carboxylic acid and a polyhydric alcohol.

Examples of the polyvalent carboxylic acid include saturated aliphatic dicarboxylic acids including succinic acid, sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids including cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid and terephthalic acid. Included are trivalent or higher valent polyvalent carboxylic acids including aromatic dicarboxylic acids, trimellitic acid, pyromellitic acid and the like, and acid anhydrides thereof and alkyl esters having 1 or more and 3 or less carbon atoms thereof. The polyvalent carboxylic acid is preferably an aliphatic dicarboxylic acid.

Examples of the polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, An aliphatic diol containing 7-heptandiol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol, etc., and a trivalent or higher valent containing glycerin, pentaerythritol, trimethylolpropane, sorbitol, etc. Alcohol etc. are included. The polyhydric alcohol is preferably an aliphatic diol.

The crystalline polyester resin may be a hybrid crystalline polyester resin. The hybrid crystalline polyester resin has a structure in which a crystalline polyester resin unit and an amorphous resin unit are chemically bonded.

The “crystalline polyester resin unit” refers to a portion of the hybrid crystalline polyester resin derived from the crystalline polyester resin. The "amorphous resin unit" refers to a portion of the hybrid crystalline polyester resin derived from a non-crystalline resin (amorphous resin).

As the crystalline polyester resin, the above-mentioned crystalline polyester resin can be used. Further, as the amorphous resin, a known amorphous resin that can be used as a binder resin for toner can be used.

In the hybrid crystalline polyester resin, the crystalline polyester resin unit and the amorphous resin unit are chemically bonded to each other, the amorphous resin units, or these resins. In the range, all of them may be arranged continuously or randomly. In addition, both units may be linked in a chain, or one chain may be graft-bonded to the other.

The chemical bond is, for example, an ester bond or a covalent bond due to an addition reaction of an unsaturated group. The hybrid crystalline polyester resin can be obtained by a known method of binding a crystalline polyester resin unit and an amorphous resin unit by chemical bonding.

The crystalline polyester resin is typically added to the binder resin as a fixing aid. Since the crystalline polyester resin as the fixing aid has a low viscosity when melted and has a high sharp melt property, the melting temperature of the binder resin and the viscosity at the time of melting are lowered, and the resin is contained in the binder resin. Makes it easier for the dispersed mold release agent to seep out of the toner matrix particles. By making it easier for the release agent to exude from the toner matrix particles in this way, the crystalline polyester resin can further enhance the effect of improving the fixing separability and the abrasion resistance of the release agent.

From the above viewpoint, the content of the crystalline polyester resin is preferably 5% by mass or more and 20% by mass or less, and more preferably 8% by mass or more and 15% by mass or less with respect to the total mass of the binder resin. preferable.

The binder resin preferably contains an amorphous resin as a main component.

The amorphous resin has substantially no crystallinity, and for example, the resin contains an amorphous portion. Examples of the amorphous resin include an amorphous polyester resin, a vinyl resin, a urethane resin, a urea resin, and a partially modified amorphous modified polyester resin. The amorphous resin can be synthesized by, for example, a known method. One type of the amorphous resin may be used alone, or two or more types may be used in combination.

The amorphous resin is preferably a vinyl resin. Vinyl-based resins are difficult to be compatible with the release agent described later. Therefore, by using the vinyl resin as the main component of the binder resin, it is possible to make it easier to finely disperse the release agent in the toner matrix particles and to make it easier for the release agent to seep out of the toner matrix particles at the time of fixing. it can.

The fact that a certain resin is the main component of the binder resin means that the content of the resin is the highest among the contents (mass basis) of all the resins contained in the binder resin. For example, when the amorphous resin is the main component of the binder resin, the content of the amorphous resin contained in the binder resin is larger than the content of the crystalline resin contained in the binder resin. Means that. Further, when the vinyl resin is the main component of the binder resin, it means that the content of the vinyl resin is the largest among the contents of each resin that can be contained in the binder resin.

The binder resin preferably contains 75% by mass or more of an amorphous resin with respect to the total mass thereof, from the viewpoint of making it easier for the release agent to exude from the toner matrix particles at the time of fixing. It is more preferable to contain 75% by mass or more of the vinyl resin with respect to the mass.

The vinyl-based resin is a resin produced by polymerization of a monomer containing a compound having a vinyl group or a derivative thereof. One type of the vinyl resin may be used alone, or two or more types may be used in combination. Examples of the vinyl-based resin include styrene- (meth) acrylic-based resin.

The styrene- (meth) acrylic resin has a molecular structure of a radical polymer of a compound having a radically polymerizable unsaturated bond. The styrene- (meth) acrylic resin can be synthesized, for example, by radical polymerization of a compound having a radically polymerizable unsaturated bond. As the compound having a radically polymerizable unsaturated bond, one kind may be used alone, or two or more kinds may be used in combination. Examples of compounds having a radically polymerizable unsaturated bond include styrene and its derivatives, and (meth) acrylic acid and its derivatives.

Examples of the above styrene and its derivatives include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, pn. -Butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4- Includes dimethylstyrene and 3,4-dichlorostyrene and the like.

Examples of the above (meth) acrylic acid and its derivatives include methyl acrylate, ethyl acrylate, butyl acrylate, -2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic. Includes butyl acetate, hexyl methacrylate, -2-ethylhexyl methacrylate, ethyl β-hydroxyacrylic acid, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

(Release agent)
The release agent contains an ester wax and a hydrocarbon wax.

When the toner matrix particles contain two types of release agents, the release agents having a higher melting point crystallize first to form crystal nuclei and have a lower melting point after exudation of these release agents from the toner matrix particles. Since the crystallization of the release agent is promoted, the crystallization of the release agent after exudation is likely to proceed. Therefore, the release agent is sufficiently crystallized after the toner image is fixed and before the paper is discharged, so that the uncrystallized mold release agent adheres to the member of the image forming apparatus in the paper discharge process or the like. , It is possible to suppress the contamination of the subsequent image due to the reattachment of the mold release agent from the member to the paper discharged later.

Since the ester wax has high wettability to the crystalline polyester resin and typically has a lower melting point, it is more likely to seep out from the toner matrix particles at the time of fixing. Therefore, the ester wax can secure the amount of the release agent exuded from the toner matrix particles at the time of fixing, and can improve the fixing separability of the toner and the scratch resistance of the formed image.

The ester wax may be any of monoester wax, diester wax, triester wax, tetraester wax and wax having 5 or more ester bonds.

Examples of the ester wax include monoesterides obtained by reacting higher fatty acids with higher alcohols, diesterates obtained by reacting higher fatty acids with dihydric alcohols or reacting higher alcohols with divalent carboxylic acids. , Triesteride of trimethylolpropane and higher fatty acid, Triesterate of glycerin and higher fatty acid, Tetraesteride of pentaerythritol and higher fatty acid, By reaction of hydroxyic acid such as citric acid with higher fatty acid or higher alcohol The obtained esterified product and an esterified product obtained by reacting an aromatic carboxylic acid or alcohol such as ring acid with a higher fatty acid or higher alcohol are included.

The hydrocarbon chain contained in the higher fatty acid and higher alcohol is preferably a hydrocarbon chain having 13 or more and 30 or less carbon atoms, and more preferably a hydrocarbon chain having 17 or more and 22 or less carbon atoms. The divalent alcohol and the divalent carboxylic acid are preferably compounds having two hydroxyl groups or two carboxyl groups at both ends of a hydrocarbon group having 1 or more and 30 or less carbon atoms.

Each of the above hydrocarbon groups is a linear or branched alkyl group, alkenyl group, alkynyl group, aromatic hydrocarbon ring group, aromatic heterocyclic group, non-aromatic hydrocarbon ring group, non-aromatic heterocycle. Group, alkoxy group, cycloalkoxy group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, acyl group, acyloxy group, amide group, carbamoyl group, ureido group, Substituted with sulfinyl group, alkylsulfonyl group, arylsulfonyl group or heteroarylsulfonyl group, amino group, halogen atom, fluorinated hydrocarbon group, cyano group, nitro group, hydroxy group, thiol group, silyl group, dear hydrogen atom, etc. It may have been done.

Specific examples of the ester wax include behenyl behenate, triglycerol behenic acid ester, pentaerythritol tetrastearic acid ester, stearyl stearate, pentaerythritol tetrabechenic acid ester, ethylene glycol stearic acid ester, ethylene glycol bechenic acid ester, and neo. Pentyl glycol stearic acid ester, neopentyl glycol behenic acid ester, 1,6-hexanediol stearic acid ester, 1,6-hexanediol behenic acid ester, glycerin stearic acid ester, glycerin behenic acid ester, stearyl citrate, behenyl citrate , Stearic acid, and behenyl ringate and the like. The ester wax may be a natural wax such as carnauba wax.

Since the hydrocarbon wax typically has a higher melting point, it is more likely to crystallize after exuding from the toner matrix particles, and itself becomes a crystal nucleus to promote the crystallization of the ester wax. Therefore, the above-mentioned hydrocarbon wax can make it difficult for the release agent to adhere to the member of the image forming apparatus.

The hydrocarbon wax may be, for example, a low molecular weight polyethylene wax, a low molecular weight polypropylene wax, a Fisher tropus wax, a microcrystalline wax, a paraffin wax or the like.

The content of the release agent is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin.

Further, the total mass (MA) of the ester wax in the toner matrix particles and the total mass (MB) of the hydrocarbon wax in the toner matrix particles preferably satisfy the following formula (3).
0.01 ≤ MB / (MA + MB) ≤ 0.3 ... Equation (3)

When MB / (MA + MB) is 0.01 or more, the hydrocarbon wax having a higher melting point is sufficiently contained in the toner matrix particles, so that the release agent exuded at the time of fixing is more easily crystallized and released. Mold adhesion is less likely to occur. Further, when MB / (MA + MB) is 0.01 or more, the amount of hydrocarbon wax having a high melting point and difficult to move in the toner becomes relatively large. Therefore, the resin particles containing no release agent are aggregated in the first step, and after the particles having a predetermined size have grown, the resin particles containing the release agent are added in the second step to further aggregate the particles. When the toner is produced (described later), the release agent added in the second step is less likely to move inward, and the surface layer side distribution ratio can be further increased. When MB / (MA + MB) is 0.3 or less, the ester wax having a lower melting point is sufficiently contained in the toner matrix particles, so that the release agent easily exudes from the toner matrix particles at the time of fixing, and the toner of the toner The low-temperature fixability, fixing separability, and scratch resistance of the formed image are further enhanced.

From the above viewpoint, MB / (MA + MB) is more preferably 0.04 or more and 0.26 or less, further preferably 0.08 or more and 0.22 or less, and 0.12 or more and 0.18 or less. Is particularly preferred.

The ester wax and the hydrocarbon wax may be used in combination by selecting any wax from the waxes described above.

It is preferable that the melting point (Tm (A)) of the ester wax satisfies the following formula (4).
65 ° C ≤ Tm (A) ≤ 80 ° C ... Equation (4)

When the melting point (Tm (A)) of the ester wax is 65 ° C. or higher, the amount of the release agent (ester wax) exuded at the time of fixing does not become too large, and the exuded mold release agent (ester wax) Can be sufficiently crystallized by the time the paper is discharged, so that the release agent can be less likely to adhere. When the melting point (Tm (A)) of the ester wax is 80 ° C. or lower, the release agent (ester wax) can be sufficiently exuded at the time of fixing, so that the fixing separability of the toner and the resistance of the formed image are tolerated. The rubbing property can be further enhanced. Further, when the melting point (Tm (A)) of the ester wax is 80 ° C. or lower, the toner matrix particles can be more sufficiently melted at the time of fixing, so that the low temperature fixability can be further improved.

From the above viewpoint, it is more preferable that the melting point (Tm (A)) of the ester wax satisfies the following formula (4-1).
70 ° C ≤ Tm (A) ≤ 80 ° C ・ ・ ・ Equation (4-1)

Further, it is preferable that the melting point (Tm (B)) of the hydrocarbon wax satisfies the following formula (5).
80 ° C ≤ Tm (B) ≤ 95 ° C ... Equation (5)

When the melting point (Tm (B)) of the hydrocarbon wax is 80 ° C. or higher, the hydrocarbon wax is more likely to crystallize after oozing out from the toner matrix particles, and the ester wax is more likely to be crystallized. It is possible to make it more difficult for the release agent to adhere. When the melting point (Tm (B)) of the hydrocarbon wax is 95 ° C. or lower, the hydrocarbon wax can be sufficiently exuded at the time of fixing, so that the fixing separability of the toner and the scratch resistance of the formed image can be obtained. Can be further enhanced. Further, when the melting point (Tm (B)) of the hydrocarbon wax is 95 ° C. or lower, the toner matrix particles can be more sufficiently melted at the time of fixing, so that the low temperature fixability can be further improved.

From the above viewpoint, it is more preferable that the melting point (Tm (B)) of the hydrocarbon wax satisfies the following formula (5-1).
85 ° C ≤ Tm (B) ≤ 90 ° C ... Equation (5-1)

Further, the ester wax and the hydrocarbon wax are combined so that the melting point of the ester wax (Tm (A)) and the melting point of the hydrocarbon wax (Tm (B)) satisfy the relationship of the following formula (6). Is preferable.
5 ° C ≤ (Tm (B) -Tm (A)) ... Equation (6)

When the difference between Tm (B) and Tm (A) is 5 ° C. or higher, the hydrocarbon wax crystallizes sufficiently faster than the ester wax at the time of fixing, and the effect of promoting the crystallization of the ester wax as crystal nuclei is sufficient. Therefore, the crystallization of the entire release agent can proceed sufficiently quickly, and the release agent can be less likely to adhere.

Further, in the ester wax and the hydrocarbon wax, the melting point of the ester wax (Tm (A)) and the melting point of the hydrocarbon wax (Tm (B)) satisfy the relationship of the following formula (6-1). , Preferably combined.
8 ° C ≤ (Tm (B) -Tm (A)) ・ ・ ・ Equation (6-1)

The upper limit of the difference between Tm (B) and Tm (A) is not particularly limited, but can be 25 ° C.

The toner matrix particles may contain other mold release agents such as amide wax.

(Other ingredients)
The toner matrix particles may optionally contain a colorant, a charge control agent, and the like.

Examples of the colorants include carbon black, magnetic materials, pigments and dyes. One type of the colorant may be used alone, or two or more types may be used in combination.

Examples of the carbon black include channel black, furnace black, acetylene black, thermal black, lamp black and the like.

Examples of the magnetic material include ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, and compounds of ferromagnetic metals such as ferrite and magnetite.

Examples of the above pigments include C.I. I. Pigment Red 2, 3, 5, 7, 7, 15, 16, 48: 1, 48: 3, 53: 1, 57: 1, 81: 4, 122, 123, 139, 144, 149, 166, 177, 178, 208, 209, 222, 238, 269, C.I. I. Pigment Orange 31, 43, C.I. I. Pigment Yellow 3, 9, 14, 14, 17, 35, 36, 65, 74, 83, 93, 94, 98, 110, 111, 138, 139, 139, same 153, 155, 180, 181 and 185, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 15: 4, 60, and phthalocyanine pigments whose central metal is zinc, titanium, magnesium, or the like are included.

Examples of the above dyes include C.I. I. Solvent Red 1, 3, 14, 17, 17, 18, 22, 23, 49, 51, 52, 58, 63, 87, 111, 122, 127, 127, 128, 131, 145, 146, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 176, 179, pyrazolone triazole. Azo Dye, Pyrazolone Triazole Azomethin Dye, Pyrazolone Azo Dye, Pyrazolone Azomethin Dye, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Includes Solvent Blue 25, 36, 60, 70, 93, 95 and the like.

Examples of the charge control agent include niglosin dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, and salicylate metal salts or metal complexes thereof. Is done.

[External agent]
The external additive can be added from the viewpoint of controlling the fluidity and chargeability of the toner particles. As the external additive, one type may be used alone, or two or more types may be used in combination.

Examples of the external additives include silica particles, titania particles, alumina particles, zirconia particles, zinc oxide particles, chromium oxide particles, cerium oxide particles, antimony oxide particles, tungsten oxide particles, tin oxide particles, tellurium oxide particles, and oxidation. Includes manganese particles, boron oxide particles and the like.

The surface of the external additive is preferably hydrophobized. A known surface treatment agent is used for the hydrophobization treatment. One type of surface treatment agent may be used alone, or two or more types may be used in combination. Examples of surface treatment agents include silane coupling agents, silicone oils, titanate-based coupling agents, aluminate-based coupling agents, fatty acids, fatty acid metal salts, esterified products thereof and loginic acids.

Examples of the silane coupling agent include dimethyldimethoxysilane, hexamethyldisilazane (HMDS), methyltrimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane and the like. Examples of the above silicone oil include cyclic compounds, linear or branched organosiloxanes, and more specifically, organosiloxane oligomers, octamethylcyclotetrasiloxanes, decamethylcyclopentasiloxanes, and tetramethylsane. Cyclotetrasiloxane, tetravinyltetramethylcyclotetrasiloxane and the like are included.

Examples of the above-mentioned silicone oil include highly reactive silicone oils in which a modifying group is introduced into the side chain or one end, both ends, one end of the side chain, both ends of the side chain, and the like, and at least the end is modified. The type of the above-mentioned modifying group may be one kind or more. Examples of the modifying groups include alkoxy, carboxyl, carbinol, higher fatty acid modification, phenol, epoxy, (meth) acryloyl and amino.

The amount of the external additive added is preferably 0.1% by mass or more and 10.0% by mass or less, and more preferably 1.0% by mass or more and 3.0% by mass or less with respect to the entire toner particles. ..

[Toner characteristics]
The two-component developer can be produced by mixing an appropriate amount of toner particles and carrier particles. Examples of mixers used for such mixing include Nauter mixers, W cones and V-type mixers.

The size and shape of the toner particles can be appropriately determined within the range in which the effects of the present embodiment can be obtained. For example, the volume average particle size of the toner particles is 3.0 μm or more and 8.0 μm or less, and the average circularity of the toner particles is 0.920 or more and 1.000 or less.

The number average particle size of the toner particles can be measured and calculated using a device in which a computer system for data processing is connected to "Multisizer 3" (manufactured by Beckman Coulter). Further, the number average particle diameter of the toner particles can be adjusted, for example, by adjusting the temperature and stirring conditions in the production of the toner particles, the classification of the toner particles, the mixing of the classified products of the toner particles, and the like.

The average circularity of the toner particles is, for example, the circumference L1 of a circle having the same projected area as the particle image in a predetermined number of toner particles using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex). , The total circumference C calculated from the following formula (c) is divided by the predetermined number from the peripheral length L2 of the particle projection image. The average circularity of the toner particles can be adjusted, for example, by the degree of aging of the resin particles in the production of the toner particles, heat treatment of the toner particles, mixing of toner particles having different circularities, and the like.
Equation (c): C = L1 / L2

Further, the size and shape of the carrier particles can also be appropriately determined within the range in which the effects of the present embodiment can be obtained. For example, the volume average particle size of the carrier particles is 15 μm or more and 100 μm or less. The volume average particle size of the carrier particles can be measured wet using, for example, a laser diffraction type particle size distribution measuring device "HELOS KA" (manufactured by Nippon Laser Co., Ltd.). Further, the volume average particle size of the carrier particles can be adjusted by, for example, a method of controlling the particle size of the core material particles according to the production conditions of the core material particles, classification of the carrier particles, mixing of the classified products of the carrier particles, and the like.

[Manufacturing method of toner particles]
The toner matrix particles can be produced, for example, by a suspension polymerization method, an emulsion agglutination method or other known methods. Of these, the emulsion aggregation method is preferable.

In the emulsion aggregation method, a plurality of aqueous dispersions in which particles of a binder resin are dispersed in an aqueous medium are mixed, and the binder resins are aggregated to form toner matrix particles. For example, the water-based dispersion of the crystalline polyester resin particles, the water-based dispersion of the amorphous resin particles as the main component, and the water-based dispersion of the colorant particles can be mixed and aggregated. Just do it.

The aqueous dispersion means a dispersion in which dispersions (particles) are dispersed in an aqueous medium whose main component (50% by mass or more) is water. In addition to water, the aqueous medium may contain a water-soluble organic medium such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.

In the present embodiment, the above-mentioned aggregation is performed by aggregating the particles of the resin containing no release agent in the first stage, and after the particles having a predetermined size have grown, in the second stage, the resin containing the release agent Particles are added to further agglomerate. As a result, it is possible to obtain toner matrix particles in which a larger amount of release agent is distributed in a region on the surface layer side. Specifically, it is preferable that the first-stage agglutination is performed until particles having a size half the average particle size of the toner matrix particles to be produced are formed, and then the second-stage agglutination is performed.

Then, the toner particles having the external additive can be obtained by adding the external additive to the formed aggregated particles (toner base particles) and mixing them.

[Image forming device]
The toner can be applied to a normal electrophotographic image forming method. For example, it is housed in the image forming apparatus shown in FIG. 1 and used for forming a toner image on a recording medium.

The image forming apparatus 1 shown in FIG. 1 includes an image reading unit 110, an image processing unit 30, an image forming unit 40, a paper conveying unit 50, and a fixing device 60.

The image forming unit 40 has image forming units 41Y, 41M, 41C and 41K for forming an image with each color toner of Y (yellow), M (magenta), C (cyan) and K (black). Since all of these have the same configuration except for the toner to be accommodated, the symbol indicating the color may be omitted hereafter. The image forming unit 40 further has an intermediate transfer unit 42 and a secondary transfer unit 43. These correspond to transfer devices.

The image forming unit 41 includes an exposure device 411, a developing device 412, a photoconductor drum 413, a charging device 414, and a drum cleaning device 415. The photoconductor drum 413 is, for example, a negatively charged organic photoconductor. The surface of the photoconductor drum 413 has photoconductivity. The photoconductor drum 413 corresponds to a photoconductor. The charging device 414 is, for example, a corona charging device. The charging device 414 may be a contact charging device that charges a contact charging member such as a charging roller, a charging brush, or a charging blade by contacting the photoconductor drum 413. The exposure device 411 includes, for example, a semiconductor laser as a light source and a light deflector (polygon motor) that irradiates a photoconductor drum 413 with a laser beam corresponding to an image to be formed.

The developing device 412 is a developing device of a two-component developing method. In the developing apparatus 412, for example, a developing container accommodating a two-component developing agent, a developing roller (magnetic roller) rotatably arranged in the opening of the developing container, and a developing container capable of communicating the two-component developing agent. It has a partition partition for partitioning the inside, a transport roller for transporting the two-component developer on the opening side of the developing container toward the developing roller, and a stirring roller for stirring the two-component developer in the developing container. .. The developing container contains the toner as a two-component developer.

The intermediate transfer unit 42 includes an intermediate transfer belt 421, a primary transfer roller 422 that presses the intermediate transfer belt 421 against the photoconductor drum 413, a plurality of support rollers 423 including a backup roller 423A, and a belt cleaning device 426. The intermediate transfer belt 421 is stretched in a loop on a plurality of support rollers 423. By rotating at least one of the plurality of support rollers 423, the intermediate transfer belt 421 travels at a constant speed in the direction of arrow A.

The secondary transfer unit 43 has an endless secondary transfer belt 432 and a plurality of support rollers 431 including the secondary transfer roller 431A. The secondary transfer belt 432 is stretched in a loop by the secondary transfer roller 431A and the support roller 431.

The fixing device 60, for example, covers the fixing roller 62 and the outer peripheral surface of the fixing roller 62, and fixes the endless heat generating belt 63 for heating and melting the toner forming the toner image on the paper S, and the paper S. It has a roller 62 and a pressure roller 64 that presses against the heating belt 63. Paper S corresponds to a recording medium.

The image forming apparatus 1 further includes an image reading unit 110, an image processing unit 30, and a paper conveying unit 50. The image reading unit 110 includes a paper feeding device 111 and a scanner 112. The paper transport unit 50 includes a paper feed unit 51, a paper discharge unit 52, and a transport path unit 53. Paper S (standard paper, special paper) identified based on the basis weight, size, etc. is stored in the three paper feed tray units 51a to 51c constituting the paper feed unit 51 for each preset type. .. The transport path portion 53 has a plurality of transport roller pairs such as a resist roller pair 53a.

The formation of an image by the image forming apparatus 1 will be described.
The scanner 112 optically scans and reads the document D on the contact glass. The reflected light from the document D is read by the CCD sensor 112a and becomes input image data. The input image data is subjected to predetermined image processing by the image processing unit 30 and sent to the exposure apparatus 411.

The photoconductor drum 413 rotates at a constant peripheral speed. The charging device 414 uniformly charges the surface of the photoconductor drum 413 to a negative electrode property. In the exposure apparatus 411, the polygon mirror of the polygon motor rotates at high speed, and the laser beam corresponding to the input image data of each color component is developed along the axial direction of the photoconductor drum 413, and the photoconductor is developed along the axial direction. The outer peripheral surface of the drum 413 is irradiated. In this way, an electrostatic latent image is formed on the surface of the photoconductor drum 413.

In the developing apparatus 412, the toner particles are charged by stirring and transporting the two-component developing agent in the developing container, and the two-component developing agent is conveyed to the developing roller to form a magnetic brush on the surface of the developing roller. The charged toner particles electrostatically adhere to the electrostatic latent image portion of the photoconductor drum 413 from the magnetic brush. In this way, the electrostatic latent image on the surface of the photoconductor drum 413 is visualized, and a toner image corresponding to the electrostatic latent image is formed on the surface of the photoconductor drum 413.

The toner image on the surface of the photoconductor drum 413 is transferred to the intermediate transfer belt 421 by the intermediate transfer unit 42. The transfer residual toner remaining on the surface of the photoconductor drum 413 after transfer is removed by a drum cleaning device 415 having a drum cleaning blade that is in sliding contact with the surface of the photoconductor drum 413.

The intermediate transfer belt 421 is pressed against the photoconductor drum 413 by the primary transfer roller 422, so that the photoconductor drum 413 and the intermediate transfer belt 421 form a primary transfer nip for each photoconductor drum. At the primary transfer nip, toner images of each color are sequentially superimposed on the intermediate transfer belt 421 and transferred.

On the other hand, the secondary transfer roller 431A is pressed against the backup roller 423A via the intermediate transfer belt 421 and the secondary transfer belt 432. As a result, the secondary transfer nip is formed by the intermediate transfer belt 421 and the secondary transfer belt 432. Paper S passes through the secondary transfer nip. The paper S is transported to the secondary transfer nip by the paper transport unit 50. The inclination of the paper S and the adjustment of the transfer timing are performed by the resist roller portion in which the resist roller pair 53a is arranged.

When the paper S is conveyed to the secondary transfer nip, a transfer bias is applied to the secondary transfer roller 431A. By applying this transfer bias, the toner image supported on the intermediate transfer belt 421 is transferred to the paper S. The paper S on which the toner image is transferred is conveyed toward the fixing device 60 by the secondary transfer belt 432.

The fixing device 60 forms a fixing nip by the heat generating belt 63 and the pressure roller 64, and heats and pressurizes the conveyed paper S at the fixing nip portion. The toner particles constituting the toner image on the paper S are heated, and the crystal nucleating agent and the hybrid crystalline resin are rapidly melted inside the toner particles. As a result, the entire toner particles are rapidly melted with a relatively small amount of heat, and the toner is melted. The components adhere to the paper S. In the adhered molten toner component, the crystal nucleating agent and its peripheral portion are rapidly crystallized, and the entire component is rapidly solidified. In this way, the toner image is quickly fixed on the paper S with a relatively small amount of heat. The paper S on which the toner image is fixed is discharged to the outside of the machine by the paper ejection unit 52 provided with the paper ejection roller 52a. In this way, a high-quality image is formed.

The transfer residual toner remaining on the surface of the intermediate transfer belt 421 after the secondary transfer is removed by a belt cleaning device 426 having a belt cleaning blade that is in sliding contact with the surface of the intermediate transfer belt 421.

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited thereto.

[Synthetic example of amorphous polyester resin a1]
A mixed solution containing a monomer as a raw material for the following vinyl resin, a monomer having a substituent that reacts with any of the amorphous polyester resin and the vinyl resin, and a polymerization initiator was put into the dropping funnel.
Styrene 80.0 parts by mass n-Butyl acrylate 20.0 parts by mass Acrylic acid 10.0 parts by mass Di-t-butyl peroxide (polymerization initiator) 16.0 parts by mass

Further, the monomer used as a raw material for the following amorphous polyester resin was put into a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. to dissolve it.
Bisphenol A ethylene oxide 2 mol adduct 50.2 parts by mass Bisphenol A propylene oxide 2 mol adduct 249.8 parts by mass terephthalic acid 120.1 parts by mass dodecenyl succinic acid 46.0 parts by mass

Under stirring, the mixed solution contained in the dropping funnel was dropped into the four-necked flask over 90 minutes, and after aging for 60 minutes, the pressure was reduced (8 kPa) to remove unreacted monomers. .. Then, 0.4 parts by mass of Ti (OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235 ° C., the temperature was raised to 235 ° C. for 5 hours under normal pressure (101.3 kPa), and 1 under reduced pressure (8 kPa). The reaction was carried out for a while. Then, the mixture was cooled to 200 ° C., reacted under reduced pressure (20 kPa), and then the solvent was removed to obtain an amorphous polyester resin a1. The weight average molecular weight (Mw) of the obtained amorphous polyester resin a1 was 24,000, and the acid value was 18.2 mgKOH / g.

[Preparation Example of Amorphous Polyester Resin Fine Particle Dispersion A1]
108 parts by mass of the obtained amorphous polyester resin a1 was put into 64 parts by mass of methyl ethyl ketone, and the mixture was dissolved by stirring at 70 ° C. for 30 minutes. Next, 3.4 parts by mass of a 25% by mass sodium hydroxide aqueous solution was added to this solution. This solution was put into a reaction vessel having a stirrer, and 210 parts by mass of water warmed to 70 ° C. was added dropwise over 70 minutes while stirring. The liquid in the container became cloudy during the dropping, and after the entire amount was dropped, it became uniformly emulsified. When the particle size of the oil droplets of this emulsion was measured with a laser diffraction type particle size distribution measuring device "LA-750 (manufactured by HORIBA)", the volume average particle size was 90 nm.

Next, while keeping the emulsion at 70 ° C., the methyl ethyl ketone was distilled off by stirring at 15 kPa (150 mbar) under reduced pressure for 3 hours using a diaphragm type vacuum pump "V-700" (manufactured by BUCHI). , Amorphous polyester resin fine particle dispersion liquid A1 in which fine particles of amorphous polyester resin a1 were dispersed was prepared. As a result of measurement with the above particle size distribution measuring device, the volume average particle size of the amorphous polyester resin fine particles in the amorphous polyester resin fine particle dispersion A1 was 94 nm.

[Synthetic example of crystalline polyester resin c1]
The monomer used as a raw material for the following crystalline polyester resin was put into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube.
200 parts by mass of tetradecanedioic acid 1,6-hexanediol 102 parts by mass

After replacing the inside of the reaction vessel with dry nitrogen gas, the temperature of the reaction system was raised to 190 ° C. over 1 hour. After confirming that the inside of the reaction system was uniformly stirred, 0.3 parts by mass of Ti (OBu) ₄ was added as a catalyst, and the temperature of the reaction system was adjusted to 190 while distilling off the generated water. A crystalline polyester resin c1 was obtained by raising the temperature from ° C. to 240 ° C. over 6 hours and continuing the dehydration condensation reaction for 6 hours while maintaining the temperature at 240 ° C. to carry out the polymerization reaction. The crystalline polyester resin c1 had a weight average molecular weight (Mw) of 18,000, an acid value of 20.1 mgKOH / g, and a melting point of 78.0 ° C.

[Preparation example of crystalline polyester resin fine particle dispersion C1]]
174.3 parts by mass of the obtained crystalline polyester resin c1 was added to 102 parts by mass of methyl ethyl ketone, and the mixture was dissolved by stirring at 75 ° C. for 30 minutes. Next, 3.1 parts by mass of a 25% by mass sodium hydroxide aqueous solution was added to this solution. This solution was put into a reaction vessel having a stirrer, and 375 parts by mass of water warmed to 70 ° C. was added dropwise over 70 minutes while stirring. The liquid in the container became cloudy during the dropping, and after dropping the entire amount, a uniformly emulsified state was obtained.

Next, while keeping the emulsion at 70 ° C., methyl ethyl ketone was distilled off by stirring at 15 kPa (150 mbar) under reduced pressure for 3 hours using a diaphragm type vacuum pump “V-700” (manufactured by BUCHI). After that, the mixture was cooled at a cooling rate of 6 ° C./min to prepare a crystalline polyester resin fine particle dispersion C1 in which fine particles of the crystalline polyester resin c1 were dispersed. As a result of measurement with the above particle size distribution measuring device, the volume average particle size of the crystalline polyester resin fine particles in the crystalline polyester resin fine particle dispersion C1 was 202 nm.

[Preparation example of colorant fine particle dispersion]
420 parts by mass of copper phthalocyanine (CI Pigment Blue 15: 3) was gradually added while stirring the solution in which 90 parts by mass of sodium dodecyl sulfate was added to 1600 parts by mass of ion-exchanged water. Then, a colorant fine particle dispersion was prepared by dispersion treatment using a stirrer Clairemix (manufactured by M-Technique Co., Ltd., "Clearmix" is a registered trademark of the same company). The colorant particles in the dispersion had a volume-based median diameter of 110 nm.

[Preparation Example of Vinyl Resin Fine Particle Dispersion S1]
(First stage polymerization)
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introduction device, 8 parts by mass of sodium dodecyl sulfate and 3000 parts by mass of ion-exchanged water were charged, and the mixture was stirred at a stirring rate of 230 rpm under a nitrogen stream. , The internal temperature was raised to 80 ° C. After raising the temperature, a solution prepared by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added, the liquid temperature was set to 80 ° C. again, and a mixed solution of the following monomers was added dropwise over 1 hour. ..
Styrene 480.0 parts by mass n-Butyl acrylate 250.0 parts by mass Methacrylic acid 68.0 parts by mass

After dropping the above mixed solution, the monomer was polymerized by heating and stirring at 80 ° C. for 2 hours to prepare a vinyl resin fine particle dispersion s1.

(Second stage polymerization)
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introduction device, 1000 parts by mass of ion-exchanged water and 55 parts by mass in terms of solid content are dispersed in vinyl resin fine particles prepared by the above first-stage polymerization. Liquid s1 was charged and heated to 87 ° C.

A mechanical disperser CLEARMIX (manufactured by M-Technique Co., Ltd.) having a circulation path for a mixed solution in which the following monomer and chain transfer agent (n-octyl-3-mercaptopropionate) are dissolved at 80 ° C. ) Was carried out for 10 minutes to prepare a dispersion containing emulsified particles (oil droplets). This dispersion was added to the above 5 L reaction vessel, and a solution of the polymerization initiator in which 6.2 parts by mass of the polymerization initiator (potassium persulfate) was dissolved in 117.6 parts by mass of ion-exchanged water was added. This system was heated and stirred at 87 ° C. for 1 hour to carry out polymerization to prepare a vinyl-based resin fine particle dispersion s1'.
Styrene 293.3 parts by mass 2-ethylhexyl acrylate 108.0 parts by mass Methacrylic acid 35.0 parts by mass n-octyl-3-mercaptopropionate 4.6 parts by mass

(Third stage polymerization)
A polymerization initiator obtained by dissolving 8.3 parts by mass of a polymerization initiator (potassium persulfate) in 157.9 parts by mass of ion-exchanged water in the vinyl-based resin fine particle dispersion s1'obtained by the second-stage polymerization. Solution was added. Further, under a temperature condition of 84 ° C., a mixed solution of the following monomer and chain transfer agent was added dropwise over 90 minutes.
Styrene 420.0 parts by mass n-butyl acrylate 188.7 parts by mass Methacrylic acid 38.9 parts by mass Methyl methacrylate 60.0 parts by mass n-octyl-3-mercaptopropionate 9.6 parts by mass

After the completion of the dropping, the polymerization was carried out by heating and stirring for 2 hours. Then, the system was cooled to 28 ° C. to obtain a vinyl resin fine particle dispersion liquid S1.

[Preparation Example of Vinyl Resin Fine Particle Dispersion S2]
(Second stage polymerization)
In a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introduction device, 1200 parts by mass of ion-exchanged water and 55 parts by mass in terms of solid content are dispersed in vinyl resin fine particles prepared by the above first-stage polymerization. Liquid s1 was charged and heated to 87 ° C.

A mechanical disperser CLEARMIX having a circulation pathway for a mixed solution in which the following monomer, chain transfer agent (n-octyl-3-mercaptopropionate) and release agent are dissolved at 80 ° C. A dispersion containing emulsified particles (oil droplets) was prepared by performing a mixing and dispersing treatment for 10 minutes by Technique Co., Ltd.). This dispersion is added to the above 5 L reaction vessel, and a solution of the polymerization initiator in which 5.4 parts by mass of the polymerization initiator (potassium persulfate) is dissolved in 103 parts by mass of ion-exchanged water is added to this system. Was heated and stirred at 87 ° C. for 1 hour to carry out polymerization to prepare a vinyl-based resin fine particle dispersion s2'.
256.5 parts by mass of styrene 2-ethylhexyl acrylate 95.3 parts by mass of methacrylic acid 30.6 parts by mass of n-octyl-3-mercaptopropionate 4.0 parts by mass Release agent 1: 122.4 parts by mass of behenyl behenate Release agent 6: Hydrocarbon wax 21.6 parts by mass

(Third stage polymerization)
A solution of a polymerization initiator in which 7.3 parts by mass of a polymerization initiator (potassium persulfate) is dissolved in 138 parts by mass of ion-exchanged water in the vinyl-based resin fine particle dispersion s2'obtained by the second-stage polymerization. Was added. Further, under a temperature condition of 84 ° C., a mixed solution of the following monomer and chain transfer agent was added dropwise over 90 minutes.
Styrene 367.2 parts by mass n-butyl acrylate 165.0 parts by mass 34.0 parts by mass of methacrylic acid Methyl methacrylate 52.5 parts by mass n-octyl-3-mercaptopropionate 8.4 parts by mass

After the completion of the dropping, the polymerization was carried out by heating and stirring for 2 hours. Then, the system was cooled to 28 ° C. to obtain a vinyl resin fine particle dispersion liquid S2.

[Preparation Example of Vinyl-based Resin Fine Particle Dispersion S3 to Vinyl-based Resin Fine Particle Dispersion S20]
In the preparation example of the vinyl-based resin fine particle dispersion liquid S2, the vinyl-based resin fine particle dispersion liquid S3 to vinyl-based in the same manner except that the type and amount of the release agent in the second stage polymerization were changed to the amounts shown in Table 1. A resin fine particle dispersion S20 was obtained.

The types of mold release agents 1 to 10 shown in Table 1 are as shown in Table 2.

[Preparation example of release agent fine particle dispersion W1]
A mixture of the following release agent, anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK, "Neogen" is a registered trademark of the same company) and ion-exchanged water is heated to 110 ° C and homogenizer. (IKA: Ultra Tarax T50) is used for dispersion, and then a manton Gorin high-pressure homogenizer (Gorin) is used for dispersion treatment, and a release agent having an average particle size of 0.21 μm is dispersed. A dispersion W1 (release agent concentration: 26% by mass) was prepared.
256.5 parts by mass of styrene Release agent 1: Behenyl behenate 25.0 parts by mass Release agent 6: Hydrocarbon wax 25.0 parts by mass Anionic surfactant 5.0 parts by mass Ion-exchanged water 200.0 parts by mass

When the particle size of the particles in the release agent fine particle dispersion W1 was measured with Microtrac UPA-150 (manufactured by Nikkiso Co., Ltd.), the volume average particle size was 215 nm.

[Manufacturing example of toner 1]
225 parts by mass (in terms of solid content) of vinyl-based resin fine particle dispersion S1 and 330 parts by mass of ion-exchanged water were put into a reaction vessel equipped with a stirrer, a temperature sensor and a cooling tube. At room temperature (25 ° C.), a pH was adjusted to 10 by adding a 5 mol / L aqueous sodium hydroxide solution. Further, 40 parts by mass (in terms of solid content) of the colorant fine particle dispersion was added, and 80 parts by mass of a 50% by mass magnesium chloride aqueous solution was added at 30 ° C. for 10 minutes with stirring. After allowing the obtained dispersion to stand for 3 minutes, the temperature is raised to 80 ° C. over 60 minutes, and after reaching 80 ° C., 56 parts by mass (solid content equivalent) of the crystalline resin fine particle dispersion C1 is applied over 20 minutes. And adjust the stirring speed so that the growth rate of the particle size is 0.01 μm / min, and the volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckman) becomes 3.0 μm. I grew it up to. When the particle size reaches 3.0 μm, 225 parts by mass (in terms of solid content) of the vinyl-based resin fine particle dispersion S2 is put into the reaction vessel and stirred so that the growth rate of the particle size is 0.01 μm / min. The speed was adjusted and the particles were grown until the volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckman) was 6.0 μm.

Next, 56 parts by mass (in terms of solid content) of the amorphous polyester resin dispersion A1 was added over 30 minutes, and when the supernatant of the reaction solution became transparent, 80 parts by mass of sodium chloride was added in an amount of 300 parts by mass. An aqueous solution dissolved in ion-exchanged water was added to stop the growth of particle size. Then, the mixture is stirred at 80 ° C., the fusion of the toner particles is allowed to proceed until the average circularity of the toner particles reaches 0.970, and then the mixture is cooled at a temperature lowering rate of 0.5 ° C./min or more and the liquid is cooled down to 30 ° C. I lowered the temperature.

Next, solid-liquid separation was performed, and the dehydrated toner cake was redispersed in ion-exchanged water and solid-liquid separation was repeated three times for washing. After washing, toner particles were obtained by drying at 35 ° C. for 24 hours. To 100 parts by mass of the obtained toner particles, 0.6 parts by mass of hydrophobic silica particles (number average primary particle size: 12 nm, degree of hydrophobicity: 68) and 1.0 part by mass of hydrophobicity as an external additive. Titanium oxide particles (number average primary particle size: 20 nm, degree of hydrophobization: 63) and 1.0 parts by mass of solgel silica (number average primary particle size: 110 nm) are added, and Henshell Mixer (Nippon Coke Industries Co., Ltd.) The rotary blades were mixed at a peripheral speed of 35 mm / sec and 32 ° C. for 20 minutes. After mixing, coarse particles were removed using a 45 μm open sieve to obtain toner 1.

[Manufacturing Examples of Toner 2 to Toner 18, Toner 20 to Toner 22, and Toner 24]
Similar to the production example of toner 1, except that the type of vinyl-based fine particle dispersion to be added after the volume-based median diameter reaches 3.0 μm and the composition ratio of the binder resin are changed to those shown in Table 3. Toners 2 to 18 and toners 20 to 24 were obtained.

[Manufacturing example of toner 19]
142 parts by mass of amorphous resin fine particle dispersion A1, 20.0 parts by mass of crystalline resin fine particle dispersion C1, 4.1 parts by mass anionic in a polymerization kettle equipped with a pH meter, stirring blades, and a thermometer. Amorphous resin fine particle dispersion A1 and crystalline resin fine particles are added with a surfactant (anionic surfactant (Doufax2A1 20% aqueous solution)) and 250 parts by mass of ion-exchanged water and stirred at 140 rpm for 15 minutes. The dispersion liquid C1 was blended with the surfactant. A 15.0 parts by mass of a colorant fine particle dispersion was added thereto and mixed, and then a 0.3 M aqueous nitric acid solution was added to the mixture to adjust the pH to 4.8.

Then, using a homogenizer (manufactured by Yamato Chemical Co., Ltd., Ultra-turrax (“Ultra-turrax” is a registered trademark of the company)), while applying a shearing force at 4000 rpm, 10% of 22 parts by mass of aluminum sulfate as a coagulant. An aqueous nitric acid solution was added dropwise. Since the viscosity of the raw material mixture rapidly increased during the dropping of the coagulant, the dropping speed was slowed down when the viscosity increased so that the coagulant was not biased to one place. After the dropping of the coagulant was completed, the rotation speed was increased to 5000 rpm and the mixture was stirred for 5 minutes, and the coagulant and the raw material mixture were sufficiently mixed to form a slurry.

After that, a stirrer and a mantle heater are installed in the reaction vessel, and while adjusting the rotation speed of the stirrer so that the slurry is sufficiently agitated, the temperature rise rate is 0.2 ° C./min up to a temperature of 40 ° C., 40. After exceeding ° C., the temperature was raised at a heating rate of 0.05 ° C./min, and the particle size was measured with a Coulter Multisizer 3 (manufactured by Coulter Beckman) every 10 minutes. When the volume-based median diameter reached 3.0 μm, 18.0 parts by mass of the release agent fine particle dispersion W1 was added. 20 parts by mass of vinyl-based resin fine particle dispersion S1, 22 parts by mass of ion-exchanged water prepared by premixing and preparing to pH 3.8 while maintaining the temperature when the volume-based median diameter reaches 6.0 μm. A mixed solution of 0.8 parts by mass of an anionic surfactant (Doufax2A1 20% aqueous solution) was prepared, and the mixed solution was poured into a reaction vessel over 20 minutes and held at 50 ° C. for 30 minutes.

Then, 0.8 parts by mass of a 20% EDTA (ethylenediaminetetraacetic acid) solution was added to the reaction vessel, and then a 1 mol / L sodium hydroxide aqueous solution was added to control the pH of the raw material dispersion to 7.5. Then, while adjusting the pH to 7.5 every 5 ° C., the temperature was raised to 85 ° C. at a heating rate of 1 ° C./min and maintained at 85 ° C. Using "Sysmex FPIA-3000" (manufactured by Malvern), the fusion of particles is allowed to proceed until the circularity becomes 0.970, and then the particles are cooled at a cooling rate of 0.5 ° C./min or more and the liquid temperature is reduced to 30 ° C. or less. Was lowered.

Next, solid-liquid separation was performed, and the dehydrated toner cake was redispersed in ion-exchanged water and solid-liquid separation was repeated three times for washing. After washing, toner particles were obtained by drying at 35 ° C. for 24 hours. To 100 parts by mass of the obtained toner particles, 0.6 parts by mass of hydrophobic silica particles (number average primary particle size: 12 nm, degree of hydrophobicity: 68) and 1.0 part by mass of hydrophobicity as an external additive. Titanium oxide particles (number average primary particle size: 20 nm, degree of hydrophobization: 63) and 1.0 part by mass of solgel silica (number average primary particle size = 110 nm) are added, and Henshell mixer (manufactured by Nippon Coke Industries Co., Ltd.) ), The rotary blades were mixed at a peripheral speed of 35 mm / sec and 32 ° C. for 20 minutes. After mixing, coarse particles were removed using a 45 μm open sieve to obtain toner 19.

[Manufacturing example of toner 23]
450 parts by mass (solid content equivalent) of vinyl-based resin fine particle dispersion S12 and 330 parts by mass of ion-exchanged water were put into a reaction vessel equipped with a stirrer, a temperature sensor and a cooling tube. At room temperature (25 ° C.), a pH was adjusted to 10 by adding a 5 mol / L aqueous sodium hydroxide solution. Further, 40 parts by mass (in terms of solid content) of the colorant fine particle dispersion was added, and 80 parts by mass of a 50% by mass magnesium chloride aqueous solution was added at 30 ° C. for 10 minutes with stirring. After allowing the obtained dispersion to stand for 3 minutes, the temperature is raised to 80 ° C. over 60 minutes, and after reaching 80 ° C., 56 parts by mass (solid content equivalent) of the crystalline resin fine particle dispersion C1 is applied over 20 minutes. The stirring speed was adjusted so that the growth rate of the particle size was 0.01 μm / min, and the volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckman) became 6.0 μm. I grew it up to. After that, the toner 23 was obtained in the same manner as in the production example of the toner 1.

The composition ratio of toner 1 to toner 24, the type of dispersion liquid charged during the production of toner 1 to toner 24, and the stage when the volume-based median diameter reaches 3.0 μm, and the preparation of the dispersion liquid containing the release agent. The timing is shown in Table 3. In Table 3, "at the time of charging" indicates that "A" was charged from the beginning of aggregation of the resin particles, and "B" was charged after the particle size reached 3.0 μm.

[Toner measurement]
(Distribution rate on the surface layer side of the release agent)
A section (thickness of the section: 100 to 200 nm) of the toner particles stained with ruthenium tetroxide (RuO ₄ ) was observed using a scanning transmission electron microscope (STEM) "JSM-7401F" (manufactured by JEOL Ltd.). The surface layer distribution ratio of the mold release agent was calculated from the reflected electron image of the cross section of the toner particles.

The toner was dispersed in a photocurable resin "D-800" (manufactured by JEOL Ltd.) and then photocured to form a block. Then, using a microtome equipped with diamond teeth, a flaky sample having a thickness of 100 to 200 nm was cut out from the above block and placed on a grid with a support film for observation with a transmission electron microscope. A filter paper was laid on a 5 cmφ plastic petri dish, and a grid on which the sample was placed was placed with the side on which the sample was placed facing up.
The dyeing conditions (time, temperature, concentration and amount of dyeing agent) were adjusted so that each resin could be distinguished when observing with a transmission electron microscope. For example, 2 to 3 drops of 0.5% RuO ₄ stain solution was dropped onto two points in the petri dish, the lid was closed, the lid of the petri dish was removed, and the stain solution was allowed to stand for about 10 minutes until the stain solution was dry. .. The contrast due to the difference in shade generated when dyeing due to the difference in crystallinity was observed in the reflected electron image imaged by STEM. The lightly stained domain was designated as the release agent domain, the darkly stained domain was designated as the crystalline resin domain, and the darkest stained domain was designated as the amorphous resin domain. The total area S of the release agent domain in the STEM image was calculated, and the area S1 of the release agent domain existing in the depth range from the outer peripheral portion of the toner to the radius / 2 of the toner was calculated. Then, the ratio (%) of the area S1 to the total area S was calculated. The ratio of the area S1 to the total area S was calculated for 100 toners by the image analysis of the toner cross section, and the average value was taken as the "surface layer distribution ratio of the release agent".

(Melting point of mold release agent)
DSC measurement of toner particles was performed by differential scanning calorimetry using a differential scanning calorimeter "DSC7000X" (manufactured by Hitachi High-Tech Science) and a thermal analyzer controller "AS3 / DX" (manufactured by Hitachi High-Tech Science). Specifically, 0.5 mg of each toner is placed in a sample container for AI auto sampler φ6.8 H2.5 mm (manufactured by Hitachi High-Tech Science), and a cover for AI auto sampler (manufactured by Hitachi High-Tech Science) is used. It is sealed, set in the sample holder of "AS3 / DX", and under the measurement conditions of a measurement temperature of 0 to 200 ° C., a temperature rise rate of 10 ° C./min, and a temperature decrease rate of 10 ° C./min, Hitachi-cool-Heat. Temperature control is performed, and the 1st. The analysis was performed based on the data in Heat. An empty aluminum pan was used to measure the reference. 1st. The peak top temperature of the endothermic peak derived from the crystalline resin in Heat was defined as Tm. The peak top temperature of the peak on the highest temperature side of the endothermic peaks is the melting point Tm (B) of the hydrocarbon wax, and the peak top temperature of the peak on the high temperature side next to Tm (B) is the melting point Tm (A) of the ester wax. And said. When only one peak was present, it was determined that both the melting point Tm (A) of the ester wax and the melting point Tm (B) of the hydrocarbon wax were the peak top temperatures of the peaks.

(Peak intensity P1 of absorption maximum peak)
Toner with 0.24 g of an external additive was pressure-molded by applying a pressure of 14 MPa for 30 seconds with a compression molding machine (SSP-10A: manufactured by Shimadzu Corporation) to obtain columnar pellets having a diameter of 10 mm. The prepared pellets were placed on a glass plate, placed in a constant temperature bath (FC-410: manufactured by ADVANTEC) set at 100 ° C., and then allowed to stand for 60 minutes. After that, the sample was taken out, and an absorption spectrum was obtained by a microscopic ATR method using an infrared spectrophotometer (IRT-5200: manufactured by JASCO Corporation). With respect to the obtained spectrum, the peak intensity P1 was calculated by the following method for the absorption maximum peak existing in the range of 2900 cm ^-1 or more and 2930 cm ^-1 or less in the absorbed wave number without correction.

The both ends of the absorption maximum peak at 2900 cm ^-1 or 2930 cm ^-1 or less, determined falling peak point absorbance decreases to (Fp1, Fp2). The maximum rising peak point of the absorption maximum peak is Mp, the line segment connecting Fp1 and Fp2 is the baseline, and the absorbance at the intersection of the perpendicular line and the baseline drawn from Mp toward the horizontal axis (wavenumber axis). The absolute value of the difference between the absorbance at Mp and the absolute value was defined as the peak intensity P1 of the absorption maximum peak.

The measurement conditions are as follows.
Prism: Ge prism Light source: Standard light source Detector: MCT_N
Resolution: 4.0 cm ^-1
Pressure: 0.2 MPa
Sensitivity, aperture diameter, interferometer speed, filter: Auto
Vertical axis: Abs. (Sample), Single (background)
Measuring range: 4000-750 cm ^-1
Accumulation number: 32 times

Composition of mold release agent in toners 1 to 24 (type of mold release agent used as ester wax and hydrocarbon wax, ratio of total mass (MA) of ester wax to total mass MB of hydrocarbon wax (MB) / (MA + MB)), the melting point Tm (A) of the ester wax, the melting point Tm (B) of the hydrocarbon wax, the difference between Tm (B) and Tm (A) (Tm (B) -Tm (A)), and The surface layer side distribution rate) and the value of P1 are shown in Table 4.

[Creation of carrier]
(Preparation of carrier core material particles 1)
35 mol% MnO, 14.5 mol% MgO, 50 mol% Fe ₂ O ₃ , and 0.5 mol% SrO were weighed to the above ratios, mixed with water, and then 5 in a wet media mill. Grinding for hours gave a slurry. The obtained slurry was dried with a spray dryer to obtain spherical particles. After adjusting the particle size of the particles, the particles were heated at 950 ° C. for 2 hours and calcined. After pulverizing with a wet ball mill for 1 hour using stainless beads having a diameter of 0.3 cm, the zirconia beads having a diameter of 0.5 cm were further pulverized for 4 hours. 0.8% by mass of PVA was added as a binder with respect to the solid content, then granulated and dried by a spray dryer, and kept at a temperature of 1350 ° C. for 5 hours in an electric furnace for main firing. Then, it was crushed, further classified to adjust the particle size, and then the low magnetic force product was separated by magnetic force beneficiation to obtain carrier core material particles 1. The particle size of the carrier core material particles 1 was 35 μm.

(Preparation of resin 1 for coating core material)
Monomer cyclohexyl methacrylate and methyl methacrylate were added to an aqueous solution of 0.3% by mass of sodium benzenesulfonate so that the mass ratio (copolymerization ratio) was 5: 5, and the monomer was added. A coating material 1 was prepared by adding an amount of potassium persulfate corresponding to 0.5% by mass of the total amount, performing emulsion polymerization, and drying by spray drying. The weight average molecular weight of the obtained coating material 1 was 500,000.

(Preparation of carrier 1)
In a high-speed stirring mixer with horizontal stirring blades, 100 parts by mass of the carrier core material particles 1 prepared above and 4.5 parts by mass of the coating material 1 are charged as core material particles, and the peripheral speed of the horizontal rotary blade is 8 m. After mixing and stirring at 22 ° C. for 15 minutes under the condition of / sec, the mixture is mixed at 120 ° C. for 50 minutes, and the surface of the core material particles is coated with the coating material 1 by the action of mechanical impact force (mechanochemical method). , Carrier 1 was manufactured.

[Evaluation of toner]
(Preparation of developer)
For each of the produced toners 1 to 24, the carrier 1 was mixed so that the toner particle concentration was 6% by mass to prepare a developer. Mixing was carried out for 30 minutes using a V-type mixer.

(Low temperature fixability)
The fixing device of the multifunction device "bizhub PRESS (registered trademark) C1070" (manufactured by Konica Minolta Co., Ltd.) was modified so that the surface temperature (fixing temperature) of the heating roller could be changed in the range of 100 to 210 ° C. Each of the multifunction devices was loaded with a developer and evaluated.

In an environment of normal temperature and humidity (temperature 20 ° C, humidity 50% RH), the amount of adhesion on A4 size high-quality paper "CF paper (grain: 80.0 g / m ² )" (manufactured by Konica Minolta Co., Ltd.) A fixing experiment was conducted in which an image having a size of 100 mm × 100 mm was fixed by setting the temperature to 8.0 g / m ² . The fixing experiment was repeated up to 180 ° C. while changing the set fixing temperature from 110 ° C. in increments of 2 ° C. The lowest fixing temperature at which image stains due to the fixing offset were not visually confirmed was defined as the lowest fixing temperature. The low temperature fixability was evaluated according to the following criteria, and ◎ and ○ were set as pass levels.

-Evaluation criteria-
⊚: Minimum fixing temperature was less than 135 ℃ ○: Minimum fixing temperature was 135 ℃ or more and less than 140 ℃ ×: Minimum fixing temperature was 140 ℃ or more

(Fixing separability)
It is possible to change the surface temperature (fixing temperature) of the heating roller in the range of 100 to 210 ° C. for the fixing device of the multifunction device "bizhub PRESS C1070" (manufactured by Konica Minolta Co., Ltd., "bizhub PRESS" is a registered trademark of the company). I modified it so that I could do it. Each of the multifunction devices was loaded with a developer and evaluated. The surface temperature of the heating roller of the fixing device is set to 190 ° C, and in an environment of normal temperature and humidity (temperature 20 ° C, humidity 50% RH), A4 size recording paper "OK print high quality (grain:)" is conveyed by vertical feed. 52.3 g / m ² ) (manufactured by Oji Paper Co., Ltd.) ”, with a toner adhesion amount of 8.0 g / m ² , a 10 cm wide solid band image extending in the axial direction of the heating roller is fixed, and its separability is improved. Evaluation was made according to the following evaluation criteria. The fixing separability was evaluated according to the following criteria, and ◎, ○, and △ were set as pass levels.

-Evaluation criteria-
⊚: The recording paper could be separated from the heating roller without curling, and there was no image deterioration. ○: The recording paper could be separated from the heating roller without curling, but there was a slight image deterioration. It was possible to separate it from the heating roller, but white streaks were observed on the image. ×: The recording paper was wrapped around the heating roller, and the heating roller and recording paper could not be separated.

(Abrasion resistance)
In the evaluation of low-temperature fixability, the set value of the heating roller when the image stain due to the fixing offset is not visually confirmed by the low-temperature fixability test is set to + 10 ° C., and the fixing image (12-tone gradation) Image) was output. Then, the image density of the patch portion of the fixed image was measured by the Macbeth reflection densitometer "RD-918". The image density was relative to the blank paper, and the patch portion having a density of 1.00 ± 0.05 was selected as the measurement portion. This measuring part was rubbed 14 times with a load of 22 g / cm ² using plain weave bleached cotton. The image density of the measuring part was measured after rubbing, and the density ratio before and after rubbing was taken as the fixing rate. The scratch resistance was evaluated according to the following criteria, and ◎, ○, and △ were set as pass levels.
Fixation rate (%) = {(image density after rubbing) / (image density before rubbing)} x 100

-Evaluation criteria-
⊚: The fixing rate was 90% or more ○: The fixing rate was 80% or more and less than 90% Δ: The fixing rate was 70% or more and less than 80% ×: The fixing rate was less than 70%

(Temperature for eliminating mold release agent adhesion to members)
As an image forming device, a commercially available full-color multifunction device "bizhub PRESS C1070" (manufactured by Konica Minolta) is used, and A4 size coated paper "OK top" is used in an environment of normal temperature and humidity (temperature 20 ° C, humidity 50% RH). coat + (basis weight: 157.0 g / ^{m 2)} "on the (manufactured by Oji Paper Co., Ltd.), the unfixed image (toner amount: 8.0 g / ^{m 2)} was formed. Next, the fixing device of the above-mentioned multifunction device was driven externally, the surface temperature of the heating roller was set to 180 ° C., and fixing was performed. The image immediately after being fixed was placed on a hot plate heated at 110 ° C. with the image surface facing up, and the SUS plate was placed directly on the image and allowed to stand for 20 seconds. During this period, the temperature obtained by sandwiching the thermocouple between the image and the SUS plate was used as the evaluation temperature at this time. The image size and the weight of the SUS plate were selected so that the pressure applied to the image was 10 kPa. After 20 seconds, the SUS plate was separated from the image, the SUS plate on the surface in contact with the image was visually confirmed, and the presence or absence of dirt on the SUS plate was observed. The above image formation, fixing, standing, and observation were repeated by lowering the temperature of the hot plate by 2 ° C., and the evaluation temperature when the SUS plate was no longer soiled was defined as the release temperature at which the release agent adhered. The temperature at which the release agent adhered to the member was eliminated was evaluated according to the following criteria, and ◎ and ○ were set as acceptable levels.
-Evaluation criteria-
⊚: The release temperature of the release agent adhesion was 75 ° C or higher ○: The release temperature of the release agent adhesion was 70 ° C or more and less than 75 ° C Δ: The release temperature of the release agent adhesion was 65 ° C or more and less than 70 ° C. ×: The temperature at which the release agent adhered was eliminated was less than 65 ° C.

Table 5 shows the evaluation results of the low temperature fixability, fixing separability, abrasion resistance, and release temperature of the release agent adhesion of the toners 1 to 24.

As is clear from Table 5, it contains a crystalline polyester resin as a binder resin, an ester wax and a hydrocarbon wax as a release agent, and 2900 cm ^-1 to 2900 cm in the absorption spectrum measured by an infrared spectrophotometer. Toners ¹ to 19 having a peak intensity P1 of the absorption maximum peak in the range of 2930 cm ^-1 of 0.02 or more and 0.06 or less are excellent in low-temperature fixability and fixing separability, and are less likely to cause mold release agent adhesion. Moreover, an image having excellent scratch resistance could be obtained.

Further, the toners 1 to toner 4, the toner 6, the toner 7, the toner 14 and the toner 19 having a peak intensity P1 of 0.03 or more and 0.05 or less are the toner 5 and the toner 9 having a peak intensity P1 of less than 0.03. An image having better abrasion resistance than the toner 12, the toner 13, the toner 15 and the toner 17 could be obtained. It is considered that this is because the release agent was exuded more sufficiently.

Further, the toner having a peak intensity P1 of 0.03 or more and 0.05 or less has more mold release agent adhesion than toner 8, toner 10, toner 11, toner 16 and toner 18 having a peak intensity P1 greater than 0.035. It was hard to occur. It is considered that this is because the amount of the release agent exuded was appropriately suppressed.

Further, the toner 1 having a surface layer side distribution ratio of 70% or more can obtain an image having better fixing separability and excellent scratch resistance than the toner 9 having a surface layer side distribution ratio of less than 70%. did it. It is considered that this is because more of the release agent is present on the surface layer side of the toner matrix particles, so that the release agent easily exudes.

Further, the toner 11 and the toner 12 in which the total mass (MA) of the ester wax and the total mass (MB) of the hydrocarbon wax satisfy the formula (3) (0.01 ≤ MB / (MA + MB) ≤ 0.3) are , MB / (MA + MB) was less than 0.01, and the release agent was less likely to adhere than the toner 10. It is considered that this is because the crystallization of the exuded mold release agent was promoted because it contained more hydrocarbon wax.

Further, the toner 11 and the toner 12 in which the total mass (MA) of the ester wax and the total mass (MB) of the hydrocarbon wax satisfy the formula (3) (0.01 ≤ MB / (MA + MB) ≤ 0.3) are , MB / (MA + MB) was superior to the toner 13 having a greater than 0.3 in low temperature fixability and fixing separability. It is considered that this is because the content of the hydrocarbon wax is moderately low, so that the release agent is exuded more sufficiently.

Further, the melting point (Tm (A)) of the ester wax is the formula (4) (65 ° C. ≤ Tm (A) ≤ 80 ° C.) and the formula (4-1) (70 ° C. ≤ Tm (A) ≤ 80 ° C.). The filled toner 1 was less likely to cause mold release agent adhesion than the toner 14 having an ester wax melting point (Tm (A)) of less than 65 ° C. It is considered that this is because the amount of the release agent exuded was appropriately suppressed.

Further, the melting point (Tm (A)) of the ester wax is the formula (4) (65 ° C. ≤ Tm (A) ≤ 80 ° C.) and the formula (4-1) (70 ° C. ≤ Tm (A) ≤ 80 ° C.). As the toner 1 to be filled, an image having excellent low-temperature fixability and fixing separability as compared with the toner 15 having a melting point (Tm (A)) of ester wax higher than 80 ° C. and excellent abrasion resistance could be obtained. It is considered that this is because the release agent (ester wax) could be sufficiently exuded at the time of fixing, and the toner matrix particles could be sufficiently melted at the time of fixing.

Further, the toners 1 and 4 in which the melting point (Tm (B)) of the hydrocarbon wax satisfies the formula (5) (80 ° C. ≤ Tm (B) ≤ 95 ° C.) are the melting points (Tm (B)) of the hydrocarbon wax. The mold release agent was less likely to adhere than the toner 16 having a temperature of less than 80 ° C. It is considered that this is because the hydrocarbon wax is more likely to crystallize after exuding from the toner matrix particles, and the ester wax is also likely to be crystallized.

Further, the toner 1 having a hydrocarbon wax melting point (Tm (B)) satisfying the formula (5) (80 ° C. ≤ Tm (B) ≤ 95 ° C.) has a hydrocarbon wax melting point (Tm (B)) of 95. It was possible to obtain an image having excellent low-temperature fixability and fixing separability and excellent abrasion resistance as compared with the toner 17 having a temperature higher than ° C. It is considered that this is because the release agent (hydrocarbon wax) could be sufficiently exuded at the time of fixing and the toner matrix particles could be sufficiently melted at the time of fixing.

Further, the toner 1 in which the melting point of the ester wax (Tm (A)) and the melting point of the hydrocarbon wax (Tm (B)) satisfy the formulas (6) (5 ° C.≤ (Tm (B) -Tm (A))). In No. 4, the release agent was less likely to adhere than the toner 18 in which (Tm (B) -Tm (A)) was less than 5 ° C. It is considered that the hydrocarbon wax that crystallized after exuding from the toner matrix particles was able to sufficiently promote the crystallization of the ester wax.

Further, the toner 1 in which the vinyl resin is the main component of the binder resin can obtain an image having better scratch resistance than the toner 19 in which the vinyl resin is not the main component of the binder resin. It is considered that this is because the release agent was exuded more sufficiently.

On the other hand, the toner 20 which does not contain the crystalline polyester resin as the binder resin is inferior in low temperature fixability and fixing separability, and also tends to cause mold release agent adhesion. It is considered that this is because the melting temperature of the binder resin and the viscosity at the time of melting are high, and it is difficult for the release agent to seep out from the toner base particles.

Further, the toner 21 containing no hydrocarbon wax was liable to adhere to the release agent. It is considered that this is because the hydrocarbon wax that crystallized after exuding acted as a crystal nucleus, which did not promote the crystallization of the release agent.

Further, the toner 22 which does not contain ester wax and has a peak intensity P1 of less than 0.02 was inferior in abrasion resistance. It is considered that this is because the release agent having a low melting point and easily exuding is not contained in the toner matrix particles, so that the amount of the release agent exuding from the toner matrix particles is insufficient.

Further, the toner 23, which contains both ester wax and hydrocarbon wax but has a peak intensity P1 of less than 0.02, was also inferior in abrasion resistance. It is considered that this is because the amount of the release agent exuded from the toner matrix particles was insufficient.

Further, the toner 24 having a peak intensity P1 larger than 0.06 was liable to cause mold release agent adhesion. It is considered that this is because the amount of the release agent exuded from the toner matrix particles was excessive.

According to the toner of the present invention, it is possible to obtain an image having excellent low-temperature fixability and fixing separability, less likely to cause the release agent to adhere to a member of the image forming apparatus, and excellent scratch resistance. Therefore, according to the present invention, it is expected to contribute to the further spread of the electrophotographic image forming method.

1 Image forming device 30 Image processing unit 40 Image forming unit 41Y, 41M, 41C, 41K Image forming unit 42 Intermediate transfer unit 43 Secondary transfer unit 50 Paper transport unit 51 Paper feed unit 51a, 51b, 51c Paper feed tray unit 52 Discharge Paper part 52a Paper ejection roller 53 Conveyance path part 53a Resist roller vs. 60 Fixing device 62 Fixing roller 63 Heat generating belt 64 Pressurizing roller 110 Image reading unit 111 Feeding device 112 Scanner 112a CCD sensor 411 Exposure device 412 Developer 413 Photoreceptor drum 414 Charging device 415 Drum cleaning device 421 Intermediate transfer belt 422 Primary transfer roller 423, 431 Support roller 423A Backup roller 426 Belt cleaning device 431A Secondary transfer roller 432 Secondary transfer belt D Original

Claims (9)

A toner for electrostatic latent image development having toner particles containing a binder resin and a mold release agent.
The binding resin contains a crystalline polyester resin and contains
The release agent contains an ester wax and a hydrocarbon wax.
After allowing the toner to stand in an environment of 100 ° C. for 60 minutes, it is absorbed within a range in which the absorbed wavenumber is 2900 cm ^-1 or more and 2930 cm ^-1 or less in the absorption spectrum measured by the total reflection method using an infrared spectrophotometer. A toner having a maximum peak and having a peak intensity P1 of the absorption maximum peak satisfying the following formula (1).
0.02 ≤ P1 ≤ 0.06 ... Equation (1) The toner according to claim 1, wherein the peak intensity P1 satisfies the following formula (2).
0.03 ≤ P1 ≤ 0.05 ・ ・ ・ Equation (2) The toner according to claim 1 or 2, wherein 70% or more of the release agent is present in a range from the outer peripheral portion of the toner particles to a depth of 1/2 of the radius of the toner particles. The toner according to any one of claims 1 to 3, wherein the total mass (MA) of the ester wax and the total mass (MB) of the hydrocarbon wax satisfy the following formula (3).
0.01 ≤ MB / (MA + MB) ≤ 0.3 ... Equation (3) The toner according to any one of claims 1 to 4, wherein the melting point (Tm (A)) of the ester wax satisfies the following formula (4).
65 ° C ≤ Tm (A) ≤ 80 ° C ・ ・ ・ Equation (4) The toner according to any one of claims 1 to 5, wherein the melting point (Tm (A)) of the ester wax satisfies the following formula (4-1).
70 ° C ≤ Tm (A) ≤ 80 ° C ・ ・ ・ Equation (4-1) The toner according to any one of claims 1 to 5, wherein the melting point (Tm (B)) of the hydrocarbon wax satisfies the following formula (5).
80 ° C ≤ Tm (B) ≤ 95 ° C ・ ・ ・ Equation (5) The toner according to any one of claims 1 to 7, wherein the melting point of the ester wax (Tm (A)) and the melting point of the hydrocarbon wax (Tm (B)) satisfy the relationship of the following formula (6). ..
5 ° C ≤ (Tm (B) -Tm (A)) ・ ・ ・ Equation (6) The toner according to any one of claims 1 to 8, wherein the binder resin contains a vinyl resin as a main component.

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