JP2023170036A - Toner, toner set, toner storage unit, and image forming method - Google Patents

Abstract

To provide a toner that can be fixed to cloth and has excellent image robustness and heat-resistance storage properties.SOLUTION: A toner has at least maleic acid-modified polyolefin having a polypropylene block in a main chain, and silica particles. The content of the maleic acid-modified polyolefin is 5 mass% or more and 25 mass% or less relative to a mass obtained by excluding a colorant from the toner. The silica particles are present inside the toner. The average particle diameter of the silica particles is larger than 1 μm.SELECTED DRAWING: None

Description

The present invention relates to a toner, a toner set, a toner storage unit, and an image forming method.

2. Description of the Related Art In recent years, as electrophotographic color image forming apparatuses have become widespread, the uses of their printed matter have also expanded in a wide variety of ways. Particularly in the field of custom-designed consumer goods, materials that are difficult to print with conventional electrophotographic toner intended for printing on paper media (e.g. uneven substrates such as textile media such as T-shirts) The need for printing using electrophotography is increasing.

For example, with the aim of obtaining a method for manufacturing thermal transfer print sheets, etc., which can be heat-fused and adhered to the printing target without using an adhesive, and which can be obtained using toner that does not damage the crusher. , a toner made by crushing a melt-kneaded product containing a polyester resin containing a unit obtained by condensing an aliphatic carboxylic acid and an aliphatic diol, and a white pigment having a new Mohs hardness of 5 or less has been proposed (for example, , see Patent Document 1). In addition, in order to obtain a toner with excellent low-temperature fixing properties while suppressing carrier contamination, a toner matrix having sea-like domains containing amorphous polyester resin and island-like domains containing crystalline polyester resin and cellulose nanofibers has been developed. A toner including particles has been proposed (for example, see Patent Document 2). Furthermore, in order to obtain a toner for developing electrostatic images that does not have image uniformity or dust, has offset resistance and good gloss, and is free from filming, we have developed a toner that has a sea-island structure. A toner in which the amount of toner particles observed as islands is defined has been proposed (see, for example, Patent Document 3).

An object of the present invention is to provide a toner that can be fixed on cloth and has excellent image fastness and heat-resistant storage stability.

The present invention provides a toner comprising a maleic acid-modified polyolefin having at least a polypropylene block in the main chain and silica particles, wherein the content of the maleic acid-modified polyolefin is relative to the mass of the toner excluding the colorant. , 5% by mass or more and 25% by mass or less, the silica particles are present inside the toner, and the average particle diameter of the silica particles is larger than 1 μm.

According to the present invention, it is possible to provide a toner that can be fixed on cloth and has excellent image fastness and heat-resistant storage stability.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus according to an embodiment. FIG. 2 is a schematic diagram illustrating the main configuration of an image forming apparatus according to an embodiment. FIG. 3 is a schematic diagram showing another example of an image forming apparatus according to an embodiment.

Generally, images fixed on textile media must be able to be fixed on fabric fibers with many unevenness, the fixed toner layer should have appropriate flexibility, and the toner layer should not be deformed due to unevenness or deformation of the fabric. Characteristics that are not found in conventional paper medium toners are required, such as the ability to track the toner.

The present inventors have determined, with respect to toners containing polyolefins, the temperature range of the exothermic peak that appears when the temperature is lowered after the first temperature increase by DSC of the toner, and the exothermic peak that appears during the second temperature increase by DSC of the polyolefin. We focused on the temperature range. In a toner containing polyolefin, an exothermic peak appears in the range of 40 to 70 °C when the temperature is lowered after the first temperature rise by DSC of the toner, and an exothermic peak appears when the temperature is lowered after the first temperature rise by DSC of the polyolefin. If this does not occur and an exothermic peak appears in the range of 0°C to 30°C during the second temperature rise, the toner will have a low melting point and will be difficult to crystallize, resulting in poor toner fixability and fastness to cloth. It was found that there was a significant increase in However, toner manufactured using materials with a low melting point has poor heat-resistant storage stability, so there is a trade-off relationship between fixing performance and robustness and heat-resistant storage stability, and achieving both is an issue. There is.
Images obtained using the toners described in Patent Documents 1 to 3 have room for improvement in achieving both image performance such as image fastness and heat-resistant storage stability.

As a result of extensive studies, the present inventors found that by containing a predetermined amount of maleic acid-modified polyolefin having a polypropylene block in the toner, the maleic acid polyolefin functions as a low melting point adhesive, and the image quality is improved. It has been found that image performance such as image quality can be improved. Furthermore, by incorporating silica particles with an average particle diameter of more than 1 μm inside the toner, the dispersibility of the maleic acid-modified polyolefin in the toner is improved, and the amount of maleic acid-modified polyolefin exposed on the toner surface is reduced. It has been found that the heat-resistant storage stability can be improved.

Therefore, the present invention provides a toner comprising at least a maleic acid-modified polyolefin having a polypropylene block in the main chain and silica particles, wherein the content of the maleic acid-modified polyolefin is the mass of the toner excluding the colorant. 5% by mass or more and 25% by mass or less, the silica particles are present inside the toner, and the average particle diameter of the silica particles is larger than 1 μm, so that it cannot be fixed on cloth. It is possible to obtain a toner having excellent image fastness and heat-resistant storage stability.

The present invention will be explained in detail below.

(toner)
The toner of the present invention contains a maleic acid-modified polyolefin and silica particles, and may also contain other resins (A), other resins (B), and other components as necessary.
In this specification, the other resin (A) and the other resin (B) may be collectively referred to as a "binder resin."

The toner of the present invention preferably has a sea-island structure having the maleic acid-modified polyolefin as a domain.
In the sea-island structure, if the continuous phase of one component contained in the toner is expressed as a "sea" (hereinafter sometimes referred to as a matrix), the other components in the "sea" are "islands" (hereinafter sometimes referred to as a domain). It means a structure that looks like this. Note that the above-mentioned binder resin corresponds to the matrix.
In the sea-island structure of the present invention, it is preferable that the maleic acid-modified polyolefin, which is a domain, and the binder resin, which is a matrix, are in a non-compatible state, and there is no compatible portion.

<Maleic acid modified polyolefin>
The maleic acid-modified polyolefin in the present invention has at least a polypropylene block in its main chain.
The term "maleic acid-modified polyolefin" as used herein refers to a polyolefin having a polypropylene block in its main chain, whose terminal or side chain is modified with maleic acid.
Since the maleic acid-modified polyolefin having a polypropylene block in the main chain can improve the fixing property and image fastness to cloth, the toner according to one embodiment has more reliably excellent fixing property and image fastness to cloth. You can demonstrate your sexuality.

The main chain in the maleic acid-modified polyolefin is not particularly limited as long as it has a polypropylene block, and can be appropriately selected depending on the purpose. One or more selected from polypropylene blocks, polyethylene blocks, and polybutene blocks, from the viewpoint of increasing the amount of maleic acid-modified polyolefin present at the interface with the fabric during formation and fixing, thereby increasing adhesion to the fabric. It is preferable that it is a block copolymer containing.

The content of the maleic acid-modified polyolefin is 5% by mass or more and 25% by mass or less based on the mass of the toner excluding the colorant. Further, the content of the maleic acid-modified polyolefin is preferably 7% by mass or more and 22% by mass or less based on the mass of the toner excluding the colorant.
When the content of the maleic acid-modified polyolefin is 5% by mass or more based on the mass of the toner excluding the colorant, sufficient fixability to cloth can be obtained.
When the content of the maleic acid-modified polyolefin is 25% by mass or less based on the mass of the toner excluding the colorant, the maleic acid-modified polyolefin can be finely dispersed in the toner during fixing of the toner. Since the amount of maleic acid-modified polyolefin exposed on the toner surface can be reduced, heat-resistant storage stability can be maintained.

The content of the maleic acid-modified polyolefin in the toner of the present invention can be calculated from the calorific value of the exothermic peak that appears in the range of 40°C to 70°C when the toner is cooled down after the first temperature rise by DSC. can. In other words, a toner in which the content of the maleic acid-modified polyolefin in the toner is 5% by mass or more and 25% by mass or less, based on the mass of the toner excluding the colorant, has a content of 5% by mass or more and 25% by mass or less, based on the mass of the toner excluding the colorant. An exothermic peak is detected in the range of 40°C to 70°C when the temperature drops after heating.

The melting point of the maleic acid-modified polyolefin is not particularly limited and can be appropriately set depending on the purpose, but it is preferably 60°C or more and 100°C or less, more preferably 63°C or more and 95°C or less. , more preferably 65°C or more and 90°C or less.
It is preferable that the melting point of the maleic acid-modified polyolefin is 60° C. or higher, since images formed with the toner of the present invention are difficult to adhere to each other due to heat.
It is preferable for the maleic acid-modified polyolefin to have a melting point of 100° C. or lower, since this provides a toner with sufficient low-temperature fixability to cloth.
Further, when the melting point of the maleic acid-modified polyolefin is within the above-mentioned preferable range, it is possible to more easily fix the adhesive onto cloth at a lower temperature, thereby making it possible to further suppress the occurrence of curling on the cloth during fixing.

Thermal properties such as the melting point of the maleic acid-modified polyolefin can be measured with an automatic differential scanning calorimeter (eg, trade name: DSC-60A Plus, manufactured by Shimadzu Corporation).
The method for measuring the thermal properties is not particularly limited and can be appropriately selected depending on the purpose. When measuring the melting point, for example, the following method can be used.
Weigh and set 5 mg of the sample in an aluminum pan, cool it to -20°C, and then perform measurements while increasing and decreasing the temperature under the following temperature conditions. Note that the melting point refers to the endothermic peak temperature during the second temperature rise.
-Temperature conditions-
・The first temperature increase is from -20℃ to 150℃ at a temperature increase rate of 10℃/min. ・The second temperature decrease is from 150℃ to -20℃ at a temperature decrease rate of -10℃/min.・2 The second temperature increase is from -20℃ to 150℃ at a heating rate of 10℃/min.

The weight average molecular weight of the maleic acid-modified polyolefin is not particularly limited and can be set appropriately depending on the purpose, but is preferably 60,000 or more and 100,000 or less, and 65,000 or more and 90,000 or less. More preferably, it is 70,000 or more and 80,000 or less.
It is preferable that the weight average molecular weight of the maleic acid-modified polyolefin is 60,000 or more because sufficient fixability to cloth can be obtained.
When the weight average molecular weight of the maleic acid-modified polyolefin is 100,000 or less, the melting point and melt viscosity are low, so that sufficient low-temperature fixability to cloth can be obtained, which is preferable.
Further, when the weight average molecular weight of the maleic acid-modified polyolefin is within the above-mentioned preferred numerical range, the toner according to one embodiment can be easily fixed to cloth at a lower temperature, so that the cloth does not curl during fixing. It is possible to further suppress the occurrence of this phenomenon.

The weight average molecular weight of the maleic acid-modified polyolefin can be obtained by measuring the molecular weight distribution of a THF (tetrahydrofuran)-dissolved component using a gel permeation chromatography (GPC) measuring device. The GPC measurement device is not particularly limited and can be selected as appropriate depending on the purpose. For example, the product name GPC-150C (manufactured by Waters Co., Ltd.) can be used.

The column used for measuring the weight average molecular weight is not particularly limited and can be selected as appropriate depending on the purpose. KF803 (column for organic solvent-based SEC (GPC)), KF804 (column for organic solvent-based SEC (GPC)), KF805 (column for organic solvent-based SEC (GPC)), KF806 (column for organic solvent-based SEC (GPC)), Examples include organic solvent-based SEC (GPC) column) and KF807 (organic solvent-based SEC (GPC) column) (both manufactured by Showa Denko K.K.).

The method for measuring the weight average molecular weight of the maleic acid-modified polyolefin is not particularly limited and can be appropriately selected depending on the purpose. For example, the method described below can be used.
The column is stabilized in a heat chamber at 40° C., and THF is flowed as a solvent at a flow rate of 1 mL/min. Next, 0.05 g of the sample was sufficiently dissolved in 5 g of THF, and then filtered through a pretreatment filter (for example, trade name: Chromato Disc, pore size: 0.45 μm, manufactured by Kurashiki Boseki Co., Ltd.), and the final sample concentration was determined. The content is adjusted to 0.05% by mass to 0.6% by mass. After injecting 50 μL to 200 μL of the THF sample solution with the sample concentration into the column and separating the THF-dissolved content contained in the THF sample solution, a detector (for example, a differential refractive index (RI) detector) (device name: The weight average molecular weight (Mw) of the THF-dissolved component contained in the THF sample solution can be measured by converting it into a molecular weight using GPC-150C (manufactured by Waters Inc.).

To measure the weight average molecular weight of the THF-dissolved component contained in a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of a calibration curve prepared using several types of monodisperse polystyrene standard samples and the count number.
Standard polystyrene samples for creating a calibration curve include, for example, polystyrene samples manufactured by Pressure Chemical Co. or Toyo Soda Kogyo Co., Ltd. with molecular weights of 6 x 10, 2.1 x ¹⁰² , 4 x ¹⁰² , 1.75 x ¹⁰⁴ , and 1. .1×10 ⁵ , 3.9×10 ⁵ , 8.6×10 ⁵ , 2×10 ⁶ , and 4.48×10 ⁶ , and use at least 10 standard polystyrene samples. preferable.

The maleic acid modification rate in the maleic acid-modified polyolefin is not particularly limited and can be set appropriately depending on the purpose, but it is 0.5% by mass or more and 8.0% by mass based on the total amount of the maleic acid-modified polyolefin. It is preferably at least 1.0% by mass and at most 7.0% by mass, even more preferably at least 3.0% by mass and at most 6.0% by mass.
When the maleic acid modification rate in the maleic acid-modified polyolefin is within the above-mentioned preferred range, the maleic acid-modified polyolefin can ooze out to the interface between the cloth and the toner when the toner is melted, resulting in good fixing properties to the cloth. It is suitable because it can be obtained.

As the maleic acid-modified polyolefin, a suitably synthesized polyolefin may be used, or a commercially available product may be used.
The above-mentioned commercial products include, by trade name, PMA-L (substance name: maleic acid-modified polyolefin), PMA-KE (substance name: maleic acid-modified polyolefin), PMA-KH (substance name: maleic acid-modified polyolefin), Examples include PMA-T (substance name: maleic acid-modified polyolefin) (all manufactured by Toyobo Co., Ltd.).

Regarding the maleic acid-modified polyolefin contained in the toner of the present invention, the isolation, qualitative analysis, and quantitative analysis of the maleic acid-modified polyolefin are not particularly limited and can be appropriately selected depending on the purpose. It can be analyzed by various methods such as analysis, elemental analysis, DSC measurement, and other chemical analysis.
If it is difficult to analyze the toner, the toner is subjected to Soxhlet extraction using a solvent that dissolves the binder resin, such as tetrahydrofuran (THF) or toluene, and the filtrate is concentrated using an evaporator, and the maleic acid-modified polyolefin is separated. Just do the analysis. Furthermore, the analysis may be performed on samples separated by GPC and samples separated and extracted using a single solvent or a mixture of solvents.
These analysis methods may be used alone or in combination as necessary.

<Confirmation and quantification of presence of maleic acid-modified polyolefin>
Regarding the maleic acid-modified polyolefin contained in the toner of the present invention, the presence of the maleic acid-modified polyolefin is preferably confirmed and quantified using a gas chromatograph-mass spectrometer (GC-MS) or NMR (Nuclear Magnetic Resonance). be able to. Specifically, this can be carried out using the following procedures, equipment, and conditions.

<<Component analysis by GC-MS>>
-Sample preparation-
Disperse the toner in chloroform and stir overnight. Subsequently, this dispersion liquid is centrifuged and only the supernatant liquid is collected. The collected supernatant liquid is evaporated to dryness and its composition is analyzed using a gas chromatograph mass spectrometer (GC-MS). An example of measurement conditions by GC-MS is shown below. The sample is a mixture in which about 1 μL of a methylating agent (tetramethylammonium hydroxide 20% methanol solution: TMAH) is dropped into about 1 mg of the sample.

-Measurement condition-
・Pyrolysis-gas chromatograph mass spectrometry (Py-GCMS) analyzer: QP2010
(Manufactured by Shimadzu Corporation)
・Heating furnace: Py2020D
(Manufactured by Frontier Lab Co., Ltd.)
・Heating temperature: 320℃
・Column: Ultra ALLOY-5
(L=30m, I.D=0.25mm, Film=0.25μm, manufactured by GL Sciences Co., Ltd.)
・Column temperature: 50°C (holding time: 1 minute) to temperature increase (10°C/min) to 340°C (holding time: 7 minutes)
・Split ratio: 1:100
・Column flow rate: 1.0ml/min
・Ionization method: EI method (70eV)
・Measurement mode: Scan mode ・Search data: NIST 20 MASS SPECTRAL LIB.

<<Component analysis by NMR>>
-Sample preparation-
The toner is dispersed in chloroform and stirred overnight. Subsequently, this dispersion liquid is centrifuged and only the supernatant liquid is collected. The collected supernatant liquid is evaporated to dryness and used as a sample for ¹ H-NMR and ¹³ C-NMR, and its composition is analyzed by NMR. An example of a method for preparing a sample for ¹ H-NMR, a method for preparing a sample for ¹³ C-NMR, and measurement conditions is shown below.

(1) Method for preparing a sample for ¹ H-NMR Add 1 mL of d8-toluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to 100 mg of the sample, warm it with a hair dryer to dissolve it, and prepare a sample for ¹ H-NMR. Prepare.
(2) Method for preparing a sample for ^13C -NMR Add 1 mL of deuterated 1,2-dichlorotoluene (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) to 100 mg of the sample, and warm it with a hair dryer to dissolve it ^. Preparation of sample for C-NMR.

-Measurement condition-
・NMR device: ECX-500 (manufactured by JEOL Ltd.)
・Measurement nucleus = ¹ H (500MHz), measurement pulse file = single pulse dec. jxp (1H), 45℃ pulse, 20,000 integration times, Relaxation Delay - 4 seconds, data point 32K, Offset 100ppm, observation width = 250ppm, measurement temperature 70℃
-Measurement nucleus = ¹³ C (125MHz), measurement pulse file = single pulse dec. jxp (13C), 45℃ pulse, 64 integration times, Relaxation Delay 5 seconds, data points 32K, observation width = 15ppm, measurement temperature 65℃

<Silica particles>
The toner of the present invention contains silica particles inside the toner.
Note that in this specification, the silica particles contained within the toner are different from the silica used as inorganic fine particles of an external additive, which will be described later. Note that in this specification, silica particles contained within the toner may be referred to as "internally added silica."

The toner of the present invention is characterized in that the average particle diameter of the silica particles contained inside the toner is larger than 1 μm. Further, the average particle diameter of the silica particles is preferably 1 μm or more and 5 μm or less.
It is preferable that the average particle diameter of the silica particles contained in the toner of the present invention is 5 μm or less because a sufficient dispersion effect of the domains (maleic acid-modified polyolefin) can be obtained.
It is preferable that the average particle diameter of the silica particles contained in the toner of the present invention is 1 μm or more because a sufficient dispersion effect of the domains (maleic acid-modified polyolefin) can be obtained.

Examples of a method for measuring the average particle size of the silica particles contained in the toner of the present invention include a method of observing a cross section of the toner and measuring the average particle size of the silica particles. As a specific example, it can be measured using the following method.
-Measurement method of average particle diameter of silica particles-
First, for image observation, SU8230 (SEM, manufactured by Hitachi, Ltd.) and DX XFlash FlatQUAD 5060F (manufactured by Bruker) are used.
As a SEM image of a cross section of a toner, a cross section of a toner coated with carbon or Pt is photographed in EDX mode under the following conditions, and the photographing position is stored.
・Acceleration voltage: 4kv
・Emission: 20mV
・Probe current: High
・Condenser lens: 5.0
・W. D. :12.0
・Image magnification: 2000 to 5000 times according to 1 toner particle In hypermap (wide area mapping), Si element is mapped under the conditions set for at least 180 seconds, and the EDX image obtained by combining the SEM image and Si mapping information is compared. Locate. The major axis of the silica particles on the SEM image screen or on the SEM image is defined as one particle diameter of silica. The particle diameters of as many silica particles as possible are calculated within the same toner cross section, and a total of 100 to 200 silica particle diameters are measured using a plurality of images. From those average values, the average particle diameter (μm) of the silica particles can be calculated.
Note that if the accelerating voltage in EDX is too high, even silica present in the depth direction may be detected, so silica present on the toner cross section is selected as much as possible. Further, the accelerating voltage is not particularly limited as long as the silica particles present in the cross section of the toner can be sufficiently sorted, and it is also possible to set it to 2 to 5 kV or 5 to 10 kV.
Further, in the toner observed by cross-sectional observation, the number of toner containing silica particles having an average particle diameter of 1 μm or more and 5 μm or less is 60% or more of the total number of toner observed in the toner cross-section. It is preferable.

The content of the silica particles contained in the toner of the present invention is not particularly limited and can be set as appropriate depending on the purpose, but it is 4% by mass based on the mass of the toner excluding the colorant. It is preferably 30% by mass or less, more preferably 5% by mass or more and 25% by mass or less, and even more preferably 6% by mass or more and 20% by mass or less.
It is preferable that the content of the silica particles contained in the toner of the present invention is 4% by mass or more based on the mass of the toner excluding the colorant because the domain dispersion effect described below can be sufficiently obtained. be.
If the content of the silica particles contained in the toner of the present invention is 30% by mass or less based on the mass of the toner excluding the colorant, the specific gravity will increase, resulting in poor packing properties and cold offset. This is preferable because it can eliminate problems such as deterioration of smear properties and deterioration of smear properties. In addition, it is possible to solve the problems of component contamination caused by free external additives, deterioration of cleanability, deterioration of washing fastness, and deterioration of heat-resistant storage stability caused by the difficulty of immobilizing external additives, which will be described later. suitable.

The specific surface area of the silica particles contained in the toner of the present invention determined by the BET method is not particularly limited and can be set appropriately depending on the purpose, but is preferably 1 m ² /g or more and 1000 m ² /g or less, and 2 m 2 /g or more. ² /g or more and 500 m ² /g or less, more preferably 25 m ² /g or more and 500 m ² /g or less, and particularly preferably 80 m ² /g or more and 500 m ² /g or less.
When the specific surface area of the silica particles contained in the toner of the present invention measured by the BET method is 1 m ² /g or more, it is possible to effectively disperse the maleic acid-modified polyolefin and the release agent during kneading during toner production. This is suitable because it can be done.
Generally, in order to disperse organic substances such as a release agent that are incompatible with the binder resin in the toner melt during kneading into the toner, a dispersant with an adjusted SP value is added or However, if there are many organic substances that are incompatible with the binder resin, the dispersed particle size (area ratio in this specification) will become large. This may cause problems such as the particle size of the release agent being too large, or problems such as larger particles falling off during pulverization, resulting in a lower toner residual rate. In addition, in order to increase the efficiency of toner pulverization and classification and to increase the degree of immobilization of fine inorganic particles, the classified fine powder is recycled, and as a result, the inside of the toner is recycled to reduce toner loss. In some cases, the inorganic filler remains or is added to adjust the viscosity of the toner. In the present invention, in order to contain an incompatible organic substance in a larger amount than the amount of a normal mold release agent, we investigated a means with a higher dispersion effect, and as a result, we succeeded in reducing the shear stress on the dispersion in the fine region. It has been found that the necessary dispersibility can be obtained by adding specific inorganic fine particles such as silica to increase the dispersibility. Furthermore, it has been found that inorganic fine particles having a specific particle size range and a specific surface state are suitable. The shear stress increases as the particle size of the inorganic fine particles increases, but at the same time, the contact area with the melt decreases, so it tends to be insufficient for further refinement. When is within the above range, the shear stress on the dispersion becomes good, and the dispersion can be effectively dispersed when the toner is melted.

The shape and structure of the silica particles contained in the toner of the present invention are not particularly limited and can be appropriately selected depending on the purpose. That is, it is preferable that the material is porous or has a pore structure. When the silica particles have a porous shape, the bulk density becomes large, so that it is possible to prevent the specific gravity of the toner from increasing. In addition, in order to increase the contact area with the dispersion, the silica particles are particles with a porous fine uneven structure or particles with a nearly spherical shape sintered as an aggregate, and are particles that cannot be further loosened by shear stress. It is preferable that

<Other resins (A)>
In addition to the maleic acid-modified polyolefin, the toner of the present invention may contain other resins (A) as necessary. In this specification, "other resin (A)" refers to polyester resins other than maleic acid-modified polyolefin.
The other resin (A) is preferably contained as a main component in the toner of the present invention. In this specification, "contained as a main component in the toner" means that the other resin (A) is contained in the toner of the present invention based on the mass of the toner excluding the colorant. indicates that the content is 40% by mass or more. The content of the other resin (A) is preferably 45% by mass or more based on the mass of the toner excluding the colorant.
The other resin (A) can be suitably used because it provides a toner that can be fixed at low temperatures while maintaining heat-resistant storage stability.

The other resin (A) is not particularly limited and can be appropriately selected depending on the purpose, but those obtained by polycondensation of alcohol and carboxylic acid are preferred.
The alcohol is not particularly limited and can be selected as appropriate depending on the purpose, such as glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol, 1,4-bis(hydroxymeth)cyclohexane, and etherified bisphenols such as bisphenol A, other dihydric alcohol monomers, trivalent or higher polyhydric alcohol monomers, and the like.
The carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. For example, divalent organic acids such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid Acid monomer, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, and other polyvalent carboxylic acid monomers having a valence of 3 or more.

The glass transition point (glass transition temperature: Tg) of the other resin (A) is not particularly limited and can be appropriately set depending on the purpose, and is preferably 50°C or more and 75°C or less. Note that the glass transition point Tg of the other resin (A) can be measured by DSC.

<Other resins (B)>
The toner of the present invention may contain other resins (B) in addition to the maleic acid-modified polyolefin, if necessary. In addition, in this specification, "other resin (B)" shows resin other than maleic acid modified polyolefin and other resin (A).

The other resin (B) is not particularly limited and can be appropriately selected depending on the purpose, for example, styrene, poly-α-stylstyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer. Coalescence, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer , styrene resins such as styrene-α-methyl chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer (monopolymers or copolymers containing styrene or styrene substitutes), epoxy resins, vinyl chloride Examples include resins, rosin-modified maleic acid resins, phenol resins, polyethylene resins, polypropylene resins, petroleum resins, polyurethane resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins, and polyvinyl butyrate resins.

The method for producing the maleic acid-modified polyolefin, the other resin (A), and the other resin (B) is not particularly limited and can be appropriately selected depending on the purpose. For example, bulk polymerization, solution Known manufacturing methods such as polymerization, emulsion polymerization, and suspension polymerization can be used.

<Other ingredients>
The other components are not particularly limited and can be selected as appropriate depending on the purpose, and include, for example, a mold release agent, a coloring agent, a charge control agent, an external additive, a fluidity improver, a cleaning performance improver, Examples include magnetic materials.

<<Release agent>>
The mold release agent is not particularly limited and can be appropriately selected depending on the purpose, such as liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, polyolefin wax, and partial oxides and fluorides thereof. , aliphatic hydrocarbons such as chlorides; animal oils such as beef tallow and fish oil; vegetable oils such as coconut oil, soybean oil, rapeseed oil, rice bran wax, and carnauba wax; higher aliphatic alcohols such as montan wax; higher fatty acids, fatty acid amides , fatty acid bisamide, zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, zinc oleate, zinc palmitate, magnesium palmitate, zinc myristate, zinc laurate, zinc behenate, and other metal soaps; fatty acid esters; Examples include polyvinylidene fluoride. These may be used alone or in combination of two or more.
Among these, ester waxes such as fatty acid esters are preferred. If the content of the maleic acid-modified polyolefin having a polypropylene block in the main chain in the toner of the present invention is excessive, the toner and the fixing roller (or fixing belt) cannot be separated during fixing, resulting in waste jamming, that is, clogging. may occur. By containing ester wax as the mold release agent, the waste jam can be suppressed. Furthermore, the maleic acid-modified polyolefin is suitable because it can finely disperse the ester wax in the toner.

The content of the ester wax in the toner of the present invention is not particularly limited and can be set as appropriate depending on the purpose, but is 0.1% by mass or more and 8% by mass or more based on the mass of the toner excluding the colorant. The content is preferably .0% by mass or less.
When the content of the ester wax is 0.1% by mass or more based on the mass of the toner excluding the colorant, the toner and the fixing roller (or fixing belt) can be separated during fixing, It is possible to suppress the occurrence of obsolete jam, that is, clogging.
When the content of the ester wax is 8.0% by mass or less based on the mass of the toner excluding the colorant, sufficient fixability of the toner to cloth can be obtained.

<<Colorant>>
The colorant is not particularly limited, and commonly used colorants can be appropriately selected and used, such as black toner, cyan toner, magenta toner, yellow toner, white pigment, green toner, and blue toner. Examples include.

The black toner is not particularly limited and can be selected as appropriate depending on the purpose, but carbon black alone or carbon black as a main component mixed with copper phthalocyanine or the like to adjust the hue and brightness is preferred. .

The cyan toner is not particularly limited and can be appropriately selected depending on the purpose, but copper phthalocyanine, which is Pigment Blue 15:3, or a mixture of copper phthalocyanine and aluminum phthalocyanine is preferable.

The magenta toner is not particularly limited and can be appropriately selected depending on the purpose. For example, Pigment Red 53:1, Pigment Red 81, Pigment Red 122, Pigment Red 269, etc. can be used. These may be used alone or in combination of two or more.

The yellow toner is not particularly limited and can be appropriately selected depending on the purpose, but pigment yellow 74, pigment yellow 155, pigment yellow 180, pigment yellow 185, etc. can be used. These may be used alone or in combination of two or more. Among these, Pigment Yellow 185 or a mixture of Pigment Yellow 74 and Pigment Yellow 185 is preferred from the viewpoint of improving saturation and storage stability.

The white pigment is not particularly limited and can be appropriately selected depending on the purpose. For example, titanium dioxide surface-treated with silicon, zirconia, aluminum, polyol, etc. can be used.

The green toner is not particularly limited and can be appropriately selected depending on the purpose. For example, Pigment Green 7 or the like can be used, but it is necessary to pay attention to safety.

The blue toner is not particularly limited and can be appropriately selected depending on the purpose. For example, Pigment Blue 15:1, Pigment Violet 23, etc. can be used.

The toner of the present invention is preferably white or colorless and does not contain a colorant. When the toner is used as a base layer (layer formed closest to the recording medium) and a color toner layer is formed on the base layer, loss of color tone of the color toner can be reduced. .

<<<Quantitative determination of colorant>>>
The content of the colorant in the toner of the present invention can be measured as follows. Note that, here, a white coloring agent (PF739: titanium oxide) will be used as an example.
It can be calculated by creating a calibration curve as a TiO ₂ composition based on a standard sample (Ti) of a metal element specific to the colorant and quantifying it. Specifically, quantitative analysis was performed using a fluorescent X-ray device (ZSX-100e, manufactured by Rigaku Denki Kogyo Co., Ltd.) to measure the amount of metal elements in a pellet-shaped toner sample, and the content of the colorant contained in the toner was determined. You can get the amount. By subtracting the obtained content from the total mass of the toner, the "mass of the toner excluding the colorant" can be determined.

In addition, when the external additive described later has the same composition as the colorant or the same metal, the calculation can be performed by performing a peeling process on the external additive as described below.
3.75 g of toner was added to a 0.5% surfactant (Noogen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution, and stirred for 30 minutes using a tabletop roll mill at a rotation speed that did not cause foaming. Prepare dispersion A. Using an ultrasonic homogenizer (VCX750, manufactured by Sonic and Material), ultrasonic waves were applied to the obtained toner dispersion A at a height of the ultrasonic vibrating part from the bottom: 1.0 cm, an intensity of 70 W, and a duration of 1 minute. After confirming that the upper limit temperature of the liquid is 45°C or less and that the liquid temperature is in the range of 20°C to 30°C, repeat 7 sets to apply the next ultrasonic wave. Prepare toner dispersion B. The obtained toner dispersion liquid B is transferred to a centrifuge tube and centrifuged at 2000 rpm for 2 minutes. Discard the supernatant after centrifugation, add 60 mL of pure water to the precipitated toner to make a dispersed slurry, and perform suction filtration using filter paper (filter paper for Kiriyama funnel No. 5C 60φm/m, manufactured by Kiriyama Manufacturing Co., Ltd.). . The toner remaining on the filter paper is made into a dispersed slurry with 60 mL of pure water, and the filter paper is washed by suction filtration again. The toner remaining on the filter paper is collected and dried in a constant temperature bath at 40° C. for 8 hours or more. 3 g of the obtained toner was molded into pellets with a diameter of 30 mm and a thickness of 2 mm using an automatic pressure molding machine (BRE-32, manufactured by Maekawa Test Instruments Manufacturing Co., Ltd.) under the conditions of a load of 6.0 t and a pressurization time of 60 seconds. , and a toner sample after external additive removal treatment. Next, the toner that had not been subjected to the above treatment was molded into pellets having a diameter of 30 mm and a thickness of 2 mm in the same manner as toner samples before external additive removal treatment. Next, quantitative analysis is performed using a fluorescent X-ray device (ZSX-100e, manufactured by Rigaku Denki Kogyo Co., Ltd.) to measure the amount of metal elements in the pelleted toner sample.
Using the calibration curve prepared in advance, the peeling rate is calculated using the following formula.
External additive peeling rate (%) = {1-(metallic element content of toner sample after peeling treatment/metallic element content of toner sample before peeling treatment)}×100
By removing elemental components caused by external additives from these, the content of the colorant in the toner can be calculated.

The peeling rate of the external additive in the external additive peeling process is not particularly limited and may be set appropriately depending on the purpose, but it is preferable that 80% or more of the toner surface is peeled off, and 90% or more of the toner surface is peeled off. It is more preferable that you do so.

<<Charge control agent>>
The charge control agent is not particularly limited and can be appropriately selected depending on the purpose, for example, modified products of nigrosine and fatty acid metal salts, onium salts such as phosphonium salts and lake pigments thereof, triphenylmethane. Dyes and their lake pigments, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates such as dibutyltinborate, dioctyltinborate, dicyclohexyltinborate, organic metals Examples include complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acid-based metal complexes, and quaternary ammonium salts. Other charge control materials include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and their metal salts, aromatic polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. . These may be used alone or in combination of two or more.

The content of the charge control agent is not particularly limited and can be set as appropriate depending on the purpose, but it is preferably 0.1% by mass or more and 10% by mass or less based on the total amount of the binder resin. .
Furthermore, since the toner may be colored by the charge control agent, it is preferable to select a toner that is as transparent as possible, excluding black toner.

<<External additives>>
As the external additive, inorganic fine particles or the like can be used.

Inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, Examples include red pepper, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica, alumina, and titanium oxide are preferred.

The inorganic fine particles may be surface-treated with a hydrophobizing agent. Preferred examples of the hydrophobizing agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, and an aluminum coupling agent. It will be done. Also, sufficient effects can be obtained by using silicone oil as a hydrophobizing agent.

The average particle diameter of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately set depending on the purpose, but is preferably 5 nm or more and 500 nm or less, more preferably 10 nm or more and 200 nm or less.
When the average particle diameter of the primary particles of the inorganic fine particles is 5 nm or more, aggregation of the inorganic fine particles can be suppressed and the inorganic fine particles can be uniformly dispersed in the toner.
When the average particle diameter of the primary particles of the inorganic fine particles is 500 nm or less, heat-resistant storage stability can be improved due to the filler effect.
Note that the average particle diameter is a value obtained by directly determining the particle diameter from a photograph obtained by a transmission electron microscope, and it is preferable to observe at least 100 particles and use the average value of their major diameters.

<<Fluidity improver>>
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity, and can be selected as appropriate depending on the purpose. For example, silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. It will be done.
The silica and titanium oxide used as the external additives are preferably surface-treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

<<Cleanability improver>>
The cleaning performance improving agent is not particularly limited as long as it is added to the toner according to one embodiment in order to remove the developer remaining on the photoreceptor or primary transfer medium after transfer, and may be used depending on the purpose. Examples thereof include zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 μm or more and 1 μm or less.

<<Magnetic materials>>
The magnetic material is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, and the like. Among these, white ones are preferred in terms of color tone.

<Toner manufacturing method>
An example of a toner manufacturing method according to an embodiment will be described. A toner manufacturing method according to an embodiment includes a step of obtaining a mixture of binder resins (mixing step), a step of obtaining a kneaded product of the mixture (melting kneading step), and a step of obtaining a solid material of the kneaded product (solidifying step). ), a step of obtaining a pulverized solid material (fine pulverization step), and a step of classifying and recovering the pulverized material (classification step).

-Process of obtaining a mixture of binder resins (mixing process)-
First, a binder resin, a coloring agent, a diameter release agent, and if necessary, a charge control agent and the like are mixed in a mixer to obtain a mixture (mixing step).
The mixer is not particularly limited and can be selected as appropriate depending on the purpose; for example, Henschel mixer (product name: FM20B, manufactured by Nippon Coke Industries Co., Ltd.), Super Mixer (SMV-20Ba, Kawata Co., Ltd.) (manufactured by).

-Process of obtaining a kneaded mixture (melt kneading process)-
Next, the obtained mixture is melt-kneaded using a hot melt kneader to obtain a kneaded product (melt-kneading step).
The hot melt kneading machine is not particularly limited and can be selected as appropriate depending on the purpose. (manufactured by Nippon Coke Industry Co., Ltd.), a twin-screw extruder PCM co-kneader (manufactured by Busu Co., Ltd.), and an open-roll continuous kneader Kneedex (manufactured by Nippon Coke Industry Co., Ltd.).

-Process of obtaining solid material of kneaded material (solidification process)-
Next, the obtained kneaded material is cooled and solidified to obtain a solid material (solidification step). The cooling method and solidification method are not particularly limited, and any method can be used as appropriate.

-Process of obtaining a pulverized solid material (fine pulverization process)-
Next, the obtained solid material is pulverized to obtain a pulverized product (pulverization step). The solid material can be pulverized using a known pulverization method, such as a jet mill method in which the toner is included in a high-speed airflow and the solid material is pulverized by the energy generated when the toner is collided with a collision plate, or a toner method. A particle-particle collision method in which particles collide with each other in an air stream, a mechanical pulverization method in which toner is supplied between a rotor rotating at high speed and a narrow gap, and pulverized, etc. can be used.

-Process of classifying and recovering crushed material (classification process)-
Next, the pulverized material is classified to collect the pulverized material having a predetermined volume average particle size. As a result, toner can be obtained (classification step). The classification method is not particularly limited, and any suitable method can be used.

Further, the toner according to one embodiment can be manufactured using a dissolution/suspension method. When producing toner using the dissolution/suspension method, an oil phase in which toner materials such as a binder resin, a colorant, a diameter release agent, and if necessary a charge control agent are dissolved or dispersed in an organic solvent is mixed into an aqueous solution. The binder resin is reacted by dispersing it in a medium (aqueous phase). As a result, a dispersion containing a dispersion (oil droplets) containing a prepolymer in which the toner material is emulsified or dispersed is obtained. Thereafter, the organic solvent is removed from the dispersion, followed by filtration, washing, and drying, and further, if necessary, classification, etc., to produce toner base particles. A toner according to one embodiment can be obtained by granulating base particles obtained using a dissolution suspension method.

The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but organic solvents with a boiling point of less than 150° C. are preferred because they can be easily removed.

The organic solvent with a boiling point of less than 150°C is not particularly limited and can be appropriately selected depending on the purpose. Examples include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1, Examples include 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used alone or in combination of two or more.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferred, and ethyl acetate is more preferred.

The aqueous medium is not particularly limited and can be appropriately selected depending on the purpose, and includes, for example, water, water-miscible solvents, and mixtures thereof. These may be used alone or in combination of two or more. Among these, water is preferred.

The water-miscible solvent can be appropriately selected depending on the purpose, and includes, for example, alcohol, lower ketones, dimethylformamide, tetrahydrofuran, cellosolves, and the like.
The alcohol is not particularly limited and can be appropriately selected depending on the purpose, and examples include methanol, isopropanol, and ethylene glycol.
The lower ketones can be appropriately selected depending on the purpose, and include, for example, acetone, methyl ethyl ketone, and the like.

The method for removing the organic solvent from the dispersion is not particularly limited and can be selected as appropriate depending on the purpose. For example, the entire reaction system may be gradually heated to evaporate the organic solvent in the oil droplets. Examples include a method in which the organic solvent in the oil droplets is removed by spraying the dispersion into a dry atmosphere.

Classification in the above-mentioned dissolution/suspension method may be carried out by removing fine particle portions in the liquid using a cyclone, decanter, centrifugation, etc., or the classification operation may be carried out after drying.

The average particle diameter of the toner of the present invention is not particularly limited and can be set appropriately depending on the purpose, but is preferably 5 μm or more and 20 μm or less, more preferably 6 μm or more and 15 μm or less, and even more preferably 9 μm or more and 14 μm or less. .
It is preferable that the average particle diameter of the toner is within the above-mentioned preferable numerical range because it provides excellent hiding performance against an uneven substrate (recording medium such as cloth).

<Average area ratio>
The average area ratio in the present invention is preferably 0.5% or more and 2.8% or less, more preferably 0.5% or more and 2.4% or less, and even more preferably 0.5% or more and 2.25% or less. Particularly preferred is 0.6% or more and 2.25% or less.
In this specification, the term "area ratio" refers to the ratio of the area occupied by the maleic acid-modified polyolefin in the total cross-sectional area of the toner when the cross-section of the toner of the present invention is observed.
It is preferable that the average area ratio is 0.5% or more because the fixability to cloth is good.
It is preferable that the average area ratio is 2.8% or less because heat-resistant storage stability becomes good.

The average area ratio can be calculated, for example, by the following method.
First, for image observation, SU8230 (SEM, manufactured by Hitachi, Ltd.) and DX XFlash FlatQUAD 5060F (manufactured by Bruker) are used.
As for the SEM images of the toner cross section, the cross section of the toner was cut and ruthenium dyed, and about 10 images were taken as "SEM image A" with SE (U) + SE (L) under the following conditions, and the photographing positions were memorized. I'll let you.
・Acceleration voltage: 0.8kv
・Emission: 20mV
・Probe current: High
・Condenser lens: 5.0
・W. D. :12.0
・Image magnification: 2000 to 5000 times according to 1 toner particle

Next, binarization processing is performed.
The method of contrast adjustment and binarization is not particularly limited, but can be performed using image processing software Image-Pro Plus 5.1J (manufactured by MediaCybernetics).
As the setting and procedure for binarization, for example, the following steps (1) to (3) can be performed.
(1) Set Process > Enhance Contrast and specify Saturated pixels to 0.3% (2) Binarize with Process > Binary > Make Binary (3) Image > Adjust > Size: 480 * 360 pixels el±5%, Resize to 8 bits (resize only when necessary)

These binarized images are subjected to image analysis processing using image analysis software Azo-kun (manufactured by Asahi Kasei Engineering Co., Ltd.).
When you select the image analysis tab>particle analysis from the tabs, the particle analysis parameters will be displayed. When at least "area" and "equivalent circle diameter" are selected and executed as measurement items, a threshold setting screen is displayed. The threshold value may be adjusted as appropriate while viewing the image, or the threshold value automatically adjusted by image analysis software may be used as is.
Once the threshold is set, binary image correction will be displayed. While comparing (a) the image displayed by checking the "straight line separation" and "superimposition" items and (b) the image displayed by checking the "straight line separation" and "edge image" items, When image selection is performed, the number of particles, the area ratio A (%) of each toner to the total area of the photographed image, and the average of the equivalent circle diameters are calculated.

Next, the toner cross-sectional area A is calculated by manually filling in the toner cross-sectional area.
From these values, the area ratio B, which is the ratio of the area occupied by the maleic acid-modified polyolefin in the total cross-sectional area of one toner, is determined using the following formula.
(Formula)...Area ratio B (%) = (total area of photographed image/toner cross-sectional area A) x area ratio A (%)
Observe different locations within the same toner cross section, calculate the area ratio B at at least 10 points using the same procedure as above, and calculate the average area ratio B (%) in the cross section of one toner particle from the average of those values. .

At least 10 toner particle cross sections to be analyzed are selected from the 10 obtained "SEM images A", and the average area ratio B (%) is calculated for each according to the above procedure. The top two particles (two toner cross-section particles) with small and large average area ratios B (%) are removed, and the remaining average area ratios B (%) are further averaged to obtain the average area ratio C (%). This is the average area ratio in the present invention.

As described above, the toner according to one embodiment has at least a maleic acid-modified polyolefin having a polypropylene block in the main chain, and the content of the maleic acid-modified polyolefin is determined based on the mass of the toner excluding the colorant. Therefore, the toner has an exothermic peak in the range of 40°C to 70°C when the temperature is lowered after the first temperature increase by DSC, and the polyolefin There is no exothermic peak when the temperature is lowered after the temperature increase, and an exothermic peak is found in the range of 0°C to 30°C during the second temperature increase.
The toner according to one embodiment has a low melting point and can be made difficult to crystallize, so that when it is adhered to cloth, it can increase the adhesive force with the cloth and improve the fixability to the cloth. Therefore, the toner according to one embodiment can have excellent fixing properties and image fastness to cloth.

Further, since the toner according to one embodiment has a low melting point, it is possible to prevent the cloth from being heated to an unnecessarily high temperature when fixing it on the cloth. Therefore, it is possible to suppress the occurrence of curls in the cloth.

Furthermore, the toner according to one embodiment has a low melting point and can be made difficult to crystallize, so it can have excellent heat-resistant storage stability. Note that heat-resistant storage stability is evaluated based on the amount of aggregates generated in the toner after the toner is stored for a long period of time (for example, 14 days) in an environment of high temperature and high humidity (for example, 40 ° C., 70 RH%). Can be done.

If the toner according to one embodiment is used, it is possible to maintain a state fixed to the cloth, so the layer made of the toner according to one embodiment can be used as a base layer that is in direct contact with the cloth. By providing an image layer made of color toner on the base layer, the image layer can be well fixed to the cloth via the base layer.
Furthermore, since the base layer formed using the toner according to one embodiment can have appropriate flexibility, even in a medium that easily deforms, such as cloth, the base layer can deform and follow the cloth. It can be made easier. Furthermore, since the base layer formed using the toner according to one embodiment can easily follow the movement of the cloth, it is possible to suppress the base layer from peeling off from the cloth. Therefore, the image layer provided on the surface of the base layer is made less susceptible to the influence of the color of the surface of the cloth, and it is possible to suppress the loss of color reproducibility and color development that the image layer desires to produce.
Therefore, by using the toner according to one embodiment, an image with good color development can be formed on the surface of cloth, and the image formed on the surface of cloth can be stably maintained.

When a layer made of the toner according to an embodiment is used as a base layer that is in direct contact with cloth, and an image layer made of color toner is provided on the base layer, the image layer made of color toner and the cloth are provided. can improve adhesion. Therefore, the toner according to one embodiment can easily form an image with excellent fixability on cloth via the base layer.

The toner according to one embodiment can be colorless or white. Thereby, the layer made of the toner according to one embodiment can be made transparent or white. Therefore, when a layer made of the toner according to one embodiment is used as a base layer in direct contact with cloth, and an image layer formed of color toner is provided on the base layer, the image layer has the desired color reproducibility and Deterioration of color development can be suppressed. Therefore, if a layer made of the toner according to one embodiment is used as a base layer that is in direct contact with cloth, the color reproducibility and color development of the image layer can be improved.

<Developer>
The toner of the present invention can also be mixed with a carrier and the like and used as a developer. In other words, the developer includes the toner according to one embodiment of the present invention, and may also include other appropriately selected components such as a carrier, if necessary. By using the developer, a base layer with excellent fixing properties can be formed on the surface of the cloth.

The developer may be a one-component developer or a two-component developer, but when used in high-speed printers that are compatible with recent improvements in information processing speed, From this point of view, a two-component developer is preferable.

When the toner according to one embodiment is used as a one-component developer, there is little variation in the particle size of the toner even when the toner is accounted for, and there is no need to film the toner on the developing roller or use a blade that thins the toner. There is little toner adhesion to members such as, and good and stable developability and images can be obtained even during long-term agitation in a developing device.

When the toner according to one embodiment is used as a two-component developer, the toner can be mixed with a carrier. When the toner according to one embodiment is used as a two-component developer, there is little variation in the toner particle size even after long-term toner balance, and good and stable developability is achieved even during long-term agitation in a developing device. and images are obtained.

The content of the carrier in the two-component developer can be appropriately selected depending on the purpose, but is preferably 90 parts by mass or more and 98 parts by mass or less, and 93 parts by mass or more, based on 100 parts by mass of the two-component developer. More preferably, it is 97 parts by mass or less.

The developer according to one embodiment can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

<<Career>>
As the carrier, for example, magnetic fine particles can be used. Examples of the magnetic particles include spinel ferrite such as magnetite and gamma iron oxide, spinel ferrite containing one or more metals other than iron (Mn, Ni, Zn, Mg, Cu, etc.), barium ferrite, etc. Magnetoplumbite type ferrite, iron or alloy particles having an oxide layer on the surface, etc. can be used.

The volume average particle size of the core material of the carrier is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of carrier adhesion and prevention of carrier scattering, it is preferably 20 μm or more. From the viewpoint of preventing abnormal images such as streaks and deterioration of image quality, the thickness is preferably 100 μm or less. In particular, by using a core material with a volume average particle diameter of 20 to 60 μm, it is possible to more appropriately meet the recent demands for higher image quality.
Note that the volume average particle diameter can be measured using, for example, Microtrac particle size distribution analyzer model HRA9320-X100 (manufactured by Nikkiso Co., Ltd.).

The core material particles used in the carrier can be appropriately selected depending on the purpose from among those known as two-component carriers for electrophotography, as long as the magnetization satisfies a predetermined range and is a magnetic material, and the apparent density is within a predetermined value. It is preferable that the range is satisfied.
Examples of the core material particles include ferromagnetic metals such as iron and cobalt; iron oxides such as magnetite, hematite, and ferrite; various alloys and compounds; and resin particles in which these magnetic substances are dispersed in resin. . Among these, Mn-based ferrite, Mn-Mg-based ferrite, etc. are preferable from the viewpoint of environmental considerations, and Mn-Mg- ferrite is preferable from the viewpoint of forming irregularities on the surface of the core material particles and stably keeping the apparent density low. Sr ferrite is preferred.
As the core material particles, appropriately synthesized ones may be used, or commercially available products may be used.
Examples of commercial products of the core material particles include trade names such as LDC-200 (manufactured by Powder Tech Co., Ltd.) and DFC-400M (manufactured by DOWA Electronics Co., Ltd.).

In particular, when high magnetization is required as a carrier, it is preferable to use ferromagnetic fine particles such as iron as the carrier.

The shape of the carrier may be granular, spherical, or acicular.

By appropriately selecting the type and content of the carrier, a resin carrier having desired magnetization can be used. For example, as for the magnetic properties of the resin carrier, it is preferable that the strength of magnetization at 1,000 Oe is 30 emu/g to 150 emu/g.
Such resin carriers can be manufactured by spraying a molten mixture of the carrier and an insulating binder resin with a spray dryer, or by reacting and curing monomers or prepolymers in an aqueous medium in the presence of the carrier. , it is possible to produce a resin carrier in which the carrier is dispersed in a condensation type binder.

The chargeability can be controlled by fixing positively chargeable or negatively chargeable fine particles or conductive fine particles to the surface of the carrier, or by coating the carrier with a resin.
As the surface coating material (resin), silicone resin, acrylic resin, epoxy resin, fluororesin, etc. can be used. Furthermore, the coating can include positively chargeable or negatively chargeable fine particles, or conductive fine particles.
Among these, silicone resins and acrylic resins are preferred.

The weight ratio of the carrier in the developer contained in the developing device is preferably 85% by mass or more and less than 98% by mass based on the total amount of the developer.
If the weight ratio of the carrier is 85% by mass or more and less than 98% by mass with respect to the total amount of developer, scattering of toner from the developing device can be easily suppressed, and the occurrence of defective images can be reduced. Additionally, it is possible to prevent an excessive increase in the amount of charge of toner for electrophotographic development and an insufficient supply of toner for electrophotographic development, which reduces the occurrence of defective images due to a decrease in image density. can do.

(toner set)
The toner set of the present invention includes a color toner containing a binder resin and a colorant, and the toner of the present invention.

The color toner is not particularly limited, and any known color toner can be appropriately selected depending on the purpose.
The binder resin is not particularly limited and can be appropriately selected depending on the purpose. For example, the binder resin can be the same as the binder resin contained in the toner according to one embodiment.
The colorant is not particularly limited, and any known colorant can be appropriately selected depending on the purpose.

By attaching the toner set to an image forming apparatus to be described later and forming an image, image formation is performed using the toner according to an embodiment, so the toner has the characteristics of having excellent fixing properties on cloth. It is possible to form images by taking full advantage of this.

(toner storage unit)
The toner accommodating unit in the present invention refers to a unit having a function of accommodating toner, in which the toner of the present invention is accommodated. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.

The toner storage container refers to a container containing toner.
Note that when the toner is used as a developer, the toner storage container is sometimes referred to as a developer storage container.
The developer storage container is not particularly limited and can be appropriately selected from known containers, including one having a container body and a cap.

The size, structure, material, etc. of the container bodies of the toner storage container and the developer storage container are not particularly limited.
The shape of the container main body of the developer storage container is not particularly limited and can be selected as appropriate depending on the purpose, but it is preferable that the container body has a cylindrical shape such as a cylinder and has an uneven portion formed in a spiral shape on the inner circumferential surface. It is preferable to have. By rotating the container body, it becomes easier to transfer the developer content to the discharge port side. Moreover, it is more preferable that some or all of the uneven portions are formed in a bellows shape. This makes it easier for the developer to be transferred to the discharge port side.
The materials of the toner storage container and the developer storage container are not particularly limited and can be selected as appropriate depending on the purpose, but they are preferably materials with good dimensional accuracy, such as polyester resin, polyethylene resin, etc. , polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and other resin materials.

The toner storage container and the developer storage container are easy to store, transport, etc. and have excellent handling properties, so they can be removably attached to an image forming apparatus, a process cartridge, etc. to be described later, and used for replenishing toner and developer. can be used.

The developing device has means for storing and developing toner.
The process cartridge is a cartridge that integrates at least an electrostatic latent image carrier (also referred to as an image carrier) and a developing means, stores toner, and is removably attached to an image forming apparatus. The process cartridge may further include at least one selected from a charging section, an exposure section, a cleaning section, and the like.

The toner storage unit according to one embodiment accommodates the toner according to one embodiment. By attaching the toner storage unit according to one embodiment to an image forming apparatus and forming an image, the image formation is performed using the toner according to one embodiment, so the toner has excellent fixability to cloth. Image formation can be performed by taking advantage of the characteristics of

(Image forming apparatus and image forming method)
An image forming apparatus according to the present invention includes: an electrostatic latent image carrier; an electrostatic latent image forming section that forms an electrostatic latent image on the electrostatic latent image carrier; a developing section that develops the electrostatic latent image with toner to form a toner image; a transfer section that transfers the toner image to a recording medium; and a fixing section that fixes the transferred image transferred to the recording medium. , and may further include other parts as necessary.
The image forming method of the present invention includes: an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image to form a toner image; comprising a transfer step of transferring a toner image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium, the toner image being formed with the toner of the present invention, and necessary Depending on the situation, other steps may be included.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming section, and the developing step can be suitably carried out by the developing section. The transfer step can be suitably carried out by the transfer section, the fixing step can be suitably carried out by the fixing section, and the other steps can be suitably carried out by the other section. This can be carried out more suitably.

<Electrostatic latent image carrier>
The structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as "electrophotographic photoreceptor" or "photoreceptor") are not particularly limited, and may be appropriately selected from known ones. can.
The material of the electrostatic latent image carrier is not particularly limited and can be selected as appropriate depending on the purpose. OPC), etc. Among these, amorphous silicon is preferred in terms of long life.

As an amorphous silicon photoreceptor, for example, a support is heated to 50° C. to 400° C., and a vacuum evaporation method, a sputtering method, an ion plating method, a thermal CVD (Chemical Vapor Deposition) method is applied to the support. A photoreceptor having a photoconductive layer made of a-Si can be used by a film forming method such as photo-CVD, plasma CVD, or the like. Among these, the plasma CVD method, ie, a method in which a raw material gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on a support, is preferred.

The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but a cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mm or more and 100 mm or less, more preferably 5 mm or more and 50 mm or less, and 10 mm or more and 30 mm or less. The following are more preferred.

<Electrostatic latent image forming section and electrostatic latent image forming process>
The electrostatic latent image forming section in the image forming apparatus according to the present invention is not particularly limited as long as it forms an electrostatic latent image on an electrostatic latent image carrier, and may be selected as appropriate depending on the purpose. can. The electrostatic latent image forming section includes, for example, a charging device (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure device that imagewise exposes the surface of the electrostatic latent image carrier. equipment (exposure device).
The electrostatic latent image forming step in the image forming method of the present invention is a step of forming an electrostatic latent image on an electrostatic latent image carrier, and includes a charging step of charging the surface of the electrostatic latent image carrier, and a charging step of charging the surface of the electrostatic latent image carrier. and an exposure step of exposing the surface of the electrostatic latent image carrier to light to form an electrostatic latent image.
Charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using a charging device (charger).
Exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using an exposure device (exposure device).
Formation of an electrostatic latent image can be performed, for example, by uniformly charging the surface of an electrostatic latent image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming section. .

-Charging device (charger)-
The charger is not particularly limited and can be appropriately selected depending on the purpose, but includes, for example, a contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., a corotron, Examples include non-contact chargers that utilize corona discharge such as a scorotron.

The charger may have any shape other than a roller, such as a magnetic brush or a fur brush, and can be selected according to the specifications and form of the image forming apparatus.

The charger is preferably one that is disposed in contact with or in a non-contact state with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner. In addition, the charger is a charging roller that is disposed close to the electrostatic latent image carrier through a gap tape in a non-contact manner, and the surface of the electrostatic latent image carrier is It is preferable to use one that charges .

Although the charger is not limited to a contact type charger, it is preferable to use a contact type charger because an image forming apparatus in which ozone generated from the charger is reduced can be obtained.

- Exposure equipment (exposure device) -
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger in the form of an image to be formed, and can be selected as appropriate depending on the purpose. Examples of exposure devices include copying optical systems, rod lens array systems, laser optical systems, and liquid crystal shutter optical systems.

The light source used in the exposure device is not particularly limited and can be appropriately selected depending on the purpose, such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), and a semiconductor laser. (LD), electroluminescence (EL), and other light emitting materials.
Moreover, various filters such as a sharp cut filter, a band pass filter, a near-infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can also be used in order to irradiate only light in a desired wavelength range.

Note that a back-light method may be adopted in which imagewise exposure is performed from the back side of the electrostatic latent image carrier.

<Developing section and developing process>
The developing section in the image forming apparatus according to the present invention is not particularly limited as long as it can develop the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image, and may be appropriately selected depending on the purpose. can. The developing section may preferably include, for example, a developing device that accommodates toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, such as a developing device equipped with a container containing toner. is preferred.
The developing step in the image forming method of the present invention is a step of sequentially developing an electrostatic latent image with toners of a plurality of colors to form a toner image. Formation of the toner image can be performed, for example, by developing an electrostatic latent image using the toner, and can be performed using a developing device.

The toner according to one embodiment is used in the developing section and the developing process. Preferably, a toner image may be formed by using a developer containing the toner according to one embodiment and further containing other components such as a carrier as necessary.

The developer may be a monochrome developer or a multicolor developer. The developing device is, for example, a developer carrier that has a stirrer that charges the toner by frictionally stirring it, and a magnetic field generating section fixed therein, and that is rotatable while carrying a developer containing toner on its surface. A developing device having the following is preferred.

In the developing device, for example, toner and carrier are mixed and stirred, and the toner is charged by friction at that time and held in a spiked state on the surface of a rotating magnet roller, thereby forming a magnetic brush. Since the magnet roller is placed near the electrostatic latent image carrier (photoreceptor), some of the toner that makes up the magnetic brush formed on the surface of the magnet roller is absorbed by the electrostatic latent image due to the electrical attraction force. Move to the surface of the image carrier (photoreceptor). As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier (photoreceptor).

The image forming apparatus according to the present invention can include a total of five developing sections: a developing section for color toners (black, cyan, magenta, and yellow) and a developing section for the toner of the present invention. The toner of the present invention may be of any color, but is preferably colorless or white. The developing section may use some or all of black, cyan, magenta, and yellow color toners according to one embodiment.

<Transfer section and transfer process>
The transfer section in the image forming apparatus according to the present invention includes a primary transfer section that transfers a toner image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer section that transfers the composite transfer image onto a recording medium. A preferred embodiment has the following parts. Note that the intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies depending on the purpose, and suitable examples include a transfer belt and the like.
The transfer step in the image forming apparatus of the present invention is a step of transferring a toner image onto a recording medium. In the transfer step, it is preferable that an intermediate transfer member is used, and after the toner image is primarily transferred onto the intermediate transfer member, the toner image is secondarily transferred onto the recording medium.
The transfer process includes a primary transfer process in which a toner image is transferred onto an intermediate transfer body to form a composite transfer image using toner of two or more colors, preferably full color toner, and a primary transfer process in which a composite transfer image is formed on a recording medium. An embodiment including a second transfer step of transferring is more preferable.
Transfer can be performed, for example, by charging an electrostatic latent image carrier (photoreceptor) with a transfer charger, and can be performed by the transfer section.

The transfer section (the primary transfer section and the secondary transfer section) may include at least a transfer device for peeling and charging the toner image formed on the electrostatic latent image carrier (photoreceptor) toward the recording medium. preferable. The number of the transfer parts may be one, or two or more.

Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

The recording medium is typically plain paper, but there is no particular restriction as long as it can transfer the unfixed image after development, and it can be selected as appropriate depending on the purpose. A PET base for OHP or the like can also be used.

<Fixing section and fixing process>
The fixing section in the image forming apparatus according to the present invention is not particularly limited and can be appropriately selected depending on the purpose, but a known heating and pressing section is suitable. Examples of the heating and pressing section include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt, and the like.
The fixing step in the image forming apparatus of the present invention is a step of fixing the toner image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium. This may be done simultaneously for each color developer in a stacked state.

The fixing section includes a heating element including a heating element, paper or release paper that contacts the heating element, and a pressure member that presses against the heating element via the paper or release paper, and includes a film and the pressure member. It is preferable that the heating and pressing section is capable of heating and fixing a recording medium on which an unfixed image is formed by passing the recording medium therebetween.
The heating in the heating and pressurizing section is usually preferably performed at a temperature of 80°C to 200°C.
The surface pressure in the heating and pressing section is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 N/cm ² or more and 80 N/cm ² or less.

Note that in this embodiment, for example, a known optical fixing device may be used together with or in place of the fixing section depending on the purpose.

<Other parts and other processes>
In addition to the above-mentioned configuration, the image forming apparatus according to the present invention may include other sections appropriately selected as necessary, such as a static eliminator, a cleaning section, a recycling section, a control section, and the like.
In addition to the above configuration, the image forming method of the present invention can include other steps appropriately selected as necessary, such as a static elimination step, a cleaning step, and a recycling step.

<<Static elimination unit and static elimination process>>
The static eliminator is not particularly limited as long as it can apply a static eliminator bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators, such as a static eliminator. etc. are preferably mentioned.
The static elimination process is a process of applying a static elimination bias to the electrostatic latent image carrier to eliminate static electricity, and can be suitably performed by the static elimination unit.

<<Cleaning section and cleaning process>>
The cleaning section is not particularly limited as long as it can remove toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Examples of the cleaning unit include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably performed by the cleaning section.

The image forming apparatus according to the present invention can improve cleaning performance by having the cleaning section. That is, by controlling the adhesion force between toners, the fluidity of the toner can be controlled and the cleaning performance can be improved. Furthermore, by controlling the characteristics of toner after deterioration, it is possible to extend the service life and maintain excellent cleaning quality even under harsh conditions such as high temperature and humidity. Furthermore, since the external additive can be sufficiently released from the toner on the photoreceptor, high cleaning performance can be achieved by forming a deposited layer (dam layer) of the external additive at the cleaning blade nip. can.

<<Recycling Department and Recycling Process>>
The recycling section is not particularly limited, and may include known transport means.
The recycling step is a step in which the toner removed in the cleaning step is recycled to the developing section, and can be suitably carried out by the recycling section.

<<Control section>>
The control section can control the movement of each section mentioned above. The control section is not particularly limited as long as it can control the movements of each of the above sections, and can be appropriately selected depending on the purpose, and includes, for example, control devices such as a sequencer and a computer.

Since the image forming apparatus according to one embodiment can form an image using the toner according to one embodiment, it has excellent fixing properties to cloth, can suppress power consumption, and has high It is possible to stably provide high-quality images.

Here, one aspect of an image forming apparatus according to an embodiment will be described with reference to FIG. 1. However, the application of the present invention is not limited to these embodiments in any way.
In addition, in each drawing, the same components are given the same reference numerals, and duplicate explanations may be omitted. Further, the number, position, shape, etc. of the following constituent members are not limited to this embodiment, and can be set to a preferable number, position, shape, etc. for implementing the present invention.

FIG. 1 is a schematic diagram showing an example of an image forming apparatus according to an embodiment.
In the image forming apparatus shown in FIG. 1, four toner image forming units 20Y, 20C, 20M, and 20K of yellow, cyan, magenta, and black are arranged in parallel, and yellow (Y) is formed by each toner image forming unit. , cyan (C), magenta (M), and black (K) toner images to form a full-color image. Note that there is no particular restriction on the arrangement of the toner image forming portions of each color.

Each of the toner image forming sections 20Y, 20C, 20M, and 20K includes photoreceptor drums 4Y, 4C, 4M, and 4K that are rotationally driven as image carriers, respectively. Further, each of the photoreceptor drums 4Y, 4C, 4M, and 4K is provided with an exposure device 45 that forms a latent image by exposing them to laser light or LED light based on image information of each color.

Further, an intermediate transfer belt 60 serving as an intermediate transfer member is disposed so as to be movable on its surface so as to face each of the toner image forming portions 20Y, 20C, 20M, and 20K. At positions facing the photoreceptor drums 4Y, 4C, 4M, and 4K via the intermediate transfer belt 60, the toner images of each color formed on the photoreceptor drums 4Y, 4C, 4M, and 4K are transferred to the intermediate transfer belt 60. Primary transfer rollers 61Y, 61C, 61M, and 61K are arranged.

The primary transfer rollers 61Y, 61C, 61M, and 61K sequentially transfer each color toner image formed by each toner image forming section 20Y, 20C, 20M, and 20K, which will be described later, onto the intermediate transfer belt 60 and superimpose them. to form a full-color image.

A paper feed section 70 including a paper feed cassette 71, paper feed rollers 72, etc. is provided at the bottom of the image forming apparatus, and feeds the transfer paper toward registration rollers 73. The registration rollers 73 feed the transfer paper toward the opposing portion of the intermediate transfer belt 60 and the secondary transfer device 65 in synchronization with the timing of the toner image formation. The full-color toner image on the intermediate transfer belt 60 is transferred onto a transfer paper by a secondary transfer device 65, fixed by a fixing device 90, and then discharged outside the machine.

Next, each toner image forming section 20Y, 20C, 20M, and 20K will be explained. Each of the toner image forming units 20Y, 20C, 20M, and 20K has almost the same configuration and operation except for the different colors of toner stored therein, so in the following description, the subscripts Y, C, M , and K will be omitted, and the structure and operation of the toner image forming section 20 will be described. FIG. 2 is a schematic diagram illustrating the main configuration of an embodiment of an image forming apparatus.

Around the photoreceptor drum 4 of the toner image forming section 20, various means for performing an electrophotographic process, such as a charging device 40, a developing device 50, and a cleaning device 30, are arranged. A toner image of each color is formed thereon. Such a toner image forming section 20 may be a process cartridge that is formed integrally and is detachable from the main body of the image forming apparatus.

FIG. 3 shows a schematic diagram of the main part configuration of another example of an image forming apparatus including five developing means. Note that a description of points similar to those of the image forming apparatus described above will be omitted.

The image device of this embodiment includes photoconductors (photoconductor 5, photoconductor 11, photoconductor 17, photoconductor 23, photoconductor 29), and chargers (charger 6, charger 29) are provided around the photoconductor. 12, charger 18, charger 24, charger 30), developing means (developing means 8, developing means 14, developing means 20, developing means 26, developing means 32), transfer devices (transfer device 10, transfer means 16, a transfer device 22, a transfer device 28, a transfer device 34) and a cleaning device (a cleaning device 9, a cleaning device 15, a cleaning device 21, a cleaning device 27, a cleaning device 33). is irradiated with exposure light (exposure light 7, exposure light 13, exposure light 19, exposure light 25, exposure light 31).

The developing unit for each color includes the photoreceptor, the charger, the developing means, the cleaning device, and the like. The developing unit 35 uses white or transparent toner, the developing unit 36 uses black toner, the developing unit 37 uses cyan toner, the developing unit 38 uses magenta toner, and the developing unit 39 uses yellow toner to form an image and transfer it to the intermediate transfer belt 40. and create an image. The image formed on the intermediate transfer belt 40 is transferred to a recording medium by a transfer device 41 and fixed by a fixing device 43. A paper feed cassette 1 and a paper feed roller 2 are provided at the bottom of the developing unit, and feed the transfer paper toward registration rollers 3 and 4. Registration rollers 3 and 4 feed the transfer paper toward the opposing portion of intermediate transfer belt 40 and transfer device 41 in synchronization with the timing of toner image formation.

Hereinafter, the embodiments will be described in more detail with reference to Examples and Comparative Examples, but the embodiments are not limited to these Examples and Comparative Examples.

(Example 1)
[Preparation of toner 1]
<Preparation of toner base particles>
First, the material (A-1) shown in Table 1 below and the material (B-1) shown in Table 2 below were premixed using a Henschel mixer (FM20B, manufactured by Nippon Coke Industries Co., Ltd.). After that, using a single-screw kneader (Buss Co-kneader "MDK46-11D", manufactured by Buss), the raw material supply rate to the barrel was 16 kg/h, the screw temperature was 40°C, the kneading temperature was 100°C to 130°C (zone barrel temperature: The mixture was melted and kneaded at 130°C in the Z1 zone and 100°C in the Z2Z3 zone to obtain a kneaded product.
-Material (A-1)-
・Polyester resin 1:15 parts by mass (product name: EXL-101, manufactured by Sanyo Chemical Co., Ltd.)
・Polyester resin 2: 80 parts by mass (product name: RN-290, manufactured by Kao Corporation)
・Ester wax: 5 parts by mass (product name: WEP-5, manufactured by NOF Corporation)
・Maleic acid-modified polyolefin having a polypropylene block in the main chain: 20 parts by mass (product name: PMA-KH, manufactured by Toyobo Co., Ltd., melting point: 80°C, weight average molecular weight: 90,000)
・Pigment: 65 parts by mass (product name: PF-739, manufactured by Ishihara Sangyo Co., Ltd., material name: titanium oxide)
-Material (B-1)-
・Silica: 15 parts by mass (product name: P-705, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)

After the obtained kneaded product was cooled to room temperature, it was coarsely ground to 200 μm to 300 μm using a Rotoplex (manufactured by Toa Kikai Kogyo Co., Ltd.). Next, the mixture was finely pulverized using a counter jet mill (trade name: 100AFG, manufactured by Hosokawa Micron Co., Ltd.) while appropriately adjusting the pulverizing air pressure so that the mass average particle size was 8.7 μm±0.5 μm. Thereafter, the finely pulverized kneaded material was passed through an air classifier (product name: EJ-LABO, manufactured by Matsubo Co., Ltd.) so that the mass average particle size was 9.5 μm ± 0.5 μm, and the ratio of mass average particle size/number average particle size was Toner base particles 1 were obtained by classifying the particles while appropriately adjusting the louver opening so that the particle size was 1.28 or less.

<Preparation of toner 1>
Next, 1.0 parts by mass of an additive (trade name: HDK-2000 (registered trademark), manufactured by Clariant Co., Ltd., material name: silica) as an external additive, and an additive, based on the entire amount of the obtained toner base particles 1. (Product name: H05TD (registered trademark), manufactured by Clariant Co., Ltd., substance name: silica) 1.0 parts by mass was stirred and mixed using a Henschel mixer (trade name: FM20B, manufactured by Nippon Coke Industries Co., Ltd.). In this way, Toner 1 was produced.

<Measurement of average area ratio>
The average area ratio, which is the ratio of the area occupied by the maleic acid-modified polyolefin to the total cross-sectional area of the toner, was calculated. The average area ratio in Toner 1 was 1.11%. The specific measurement method will be described below.
-Measurement method of average area ratio-
First, a cross section of the obtained toner 1 was cut, and the cross section was stained with ruthenium (substance name: ruthenium tetroxide, manufactured by TAAB). Note that in the cross section of the toner, the maleic acid-modified polyolefin is dyed black by ruthenium staining, so the average area ratio of the maleic acid-modified polyolefin can be calculated by calculating the average area ratio of black areas in the toner cross section.
Using SU8230 (SEM, manufactured by Hitachi, Ltd.) and DX I took a picture and memorized the shooting position.
・Acceleration voltage: 0.8kv
・Emission: 20mV
・Probe current: High
・Condenser lens: 5.0
・W. D. :12.0
- Image magnification: 2000 to 5000 times according to one toner particle Next, binarization processing was performed using image processing software Image-Pro Plus 5.1J (manufactured by MediaCybernetics). Particle analysis was performed on the binarized image using image analysis software Azo-kun (manufactured by Asahi Kasei Engineering Co., Ltd.), and the area ratio A (%) of maleic acid-modified polyolefin in each toner to the total area of the captured image was determined. was calculated.
Next, the toner cross-sectional area A of the toner cross-sectional area was manually calculated from the binarized image.
From these values, the area ratio B, which is the ratio of the area occupied by the maleic acid-modified polyolefin to the total cross-sectional area of one toner, was determined using the following formula.
(Formula) Area ratio B (%) = (total area of photographed image/toner cross-sectional area A) x area ratio A (%)
Different locations within the same toner cross section were observed, and the area ratio B was calculated at at least 10 points using the same procedure as above, and from the average value of those values, the average area ratio B (%) in the cross section of one toner particle was calculated. .
8 to 10 cross sections of toner particles to be analyzed were selected from the 10 "SEM images A" obtained, and the average area ratio B (%) was calculated for each according to the above procedure. The average area ratio C (%) is obtained by deleting the top two sheets (two toner cross-sectional particles) of the small and large average area ratio B (%), and further averaging the remaining average area ratio B (%). It was taken as the average area ratio.

<Method for measuring average particle diameter of silica particles>
The average particle diameter of the silica particles internally added to Toner 1 was measured. The average particle diameter of the internally added silica in Toner 1 was 3.2 μm. The specific measurement method will be described below.
-Measurement method of average particle diameter of silica particles-
The obtained toner 1 was cut in cross section, subjected to carbon or Pt vapor deposition, and the cross section of the toner was photographed in EDX mode using SU8230 (SEM, manufactured by Hitachi, Ltd.) and DX XFlash FlatQUAD 5060F (manufactured by Bruker). The shooting position was memorized. Note that the shooting conditions are as follows.
・Acceleration voltage: 4kv
・Emission: 20mV
・Probe current: High
・Condenser lens: 5.0
・W. D. :12.0
・Image magnification: 2000 to 5000 times according to 1 toner particle In hypermap (wide area mapping), Si element is mapped under the conditions set for at least 180 seconds, and the EDX image obtained by combining the SEM image and Si mapping information is compared. The location was determined. The long axis of the silica particles on the SEM image screen or on the SEM image was defined as one particle diameter of the silica. The particle diameters of as many silica particles as possible were calculated within the same toner cross section, and a total of 100 silica particle diameters were measured using a plurality of images. The average particle diameter (μm) of the silica particles was calculated from those average values.

[Preparation of two-component developer]
<Preparation of carrier>
The following materials were stirred for 10 minutes using a homomixer to prepare a resin layer forming liquid.
- Acrylic resin solution (solid content concentration: 20% by mass): 200 parts - Silicone resin solution (solid content concentration: 40% by mass): 2000 parts - Silane coupling agent (solid content concentration: 100% by mass): 10 parts - Barium sulfate fine particles (volume average particle size: 480 nm): 1000 parts Tungsten-doped tin oxide fine particles (volume average particle size: 48 nm): 600 parts Toluene (volume average particle size: 48 nm): 6000 parts Volume average as carrier core material Using LDC-200 (manufactured by Powder Tech Co., Ltd.) with a particle size of 35 μm, the above resin layer forming liquid was applied to the surface of the core material using a spira coater (manufactured by Okada Seiko Co., Ltd.) so that the average thickness was 0.37 μm. It was applied at a rate of 25 g/min in an atmosphere of .degree. C., and then dried. The average thickness was adjusted by adjusting the liquid amount. The obtained carrier was fired in an electric furnace at 230° C. for 1 hour, and after cooling, it was crushed using a sieve with an opening of 100 μm to obtain carrier A.
The volume average particle diameter of the core material was measured using a Microtrac particle size analyzer (manufactured by Nikkiso Co., Ltd.) of the HRA type, with the range set at 0.7 μm or more and 125 μm or less.

<Preparation of developer 1>
Toner 1 and carrier A were uniformly mixed and charged at 48 rpm for 5 minutes using a Turbler mixer (manufactured by Willy & Backoffen (WAB)) to prepare two-component developers. Note that the mixing ratio of toner and carrier A was adjusted to the toner concentration (7% by mass) of the initial developer of the evaluation machine to obtain developer 1.

The obtained developer 1 was set in the 5th station of RICOH Pro C7200S (manufactured by Ricoh Co., Ltd.), the development and transfer conditions were adjusted with the process controller, and the release paper (product name: WoW Light 8.0, Piotec A solid image of cyan toner was applied to the image layer forming area on the image layer forming area (manufactured by Co., Ltd.) with an adhesion amount of 0.4 mg/cm ² , and then a solid image of toner 1 was developed and transferred to an image pattern with an adhesion amount of 0.45 mg/cm ² , and was fixed to form an image layer. As a result, a toner image layer was obtained on release paper with an image of 0.85±0.3 mg/cm ² with Toner 1 on the top surface. Set the dark and light T-shirt base material in a heat press machine (product name: Model HTP234PS1, manufactured by Piotec), and place the image layer facing downward, that is, the side on which toner 1 is formed, is in contact with the T-shirt, and the release paper is After stacking them so that the back side was the top surface, a load of 600 g/cm ² and heat of 120° C. were applied. After releasing the load, peel off the release paper, place silicone paper (product name: FINISH-RG, manufactured by EUROPORT) on top of the T-shirt with the image transferred, perform heat press again, and peel off the silicone sheet. An image 1 T-shirt in which an image was formed on a light and dark T-shirt was obtained.

(Examples 2 to 16)
Toners 2 to 16 were prepared in the same manner as in Example 1, except that the materials in <Preparation of toner base particles> in Example 1 were changed to the materials shown in Tables 1 to 2 above and the combinations shown in Table 3 below. , Developers 2 to 16, and Images 2 to 16 T-shirts were obtained.
In the same manner as in Example 1, the area average ratio and the average particle diameter of the silica particles were measured and shown in Table 5.
The details of materials (B-2) to (B-8) shown in Table 2 are as follows.
-Materials (B-2) to (B-8)-
・Material (B-2): Silica (product name: P-527, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)
・Material (B-3): Silica (product name: P-803, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)
・Material (B-4): Silica (product name: P-603, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)
・Material (B-5): Silica (product name: SO-E6, manufactured by Admatechs Company Limited, structure: spherical)
・Material (B-6): Silica (product name: P50, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)
・Material (B-7): Silica (product name: P526, manufactured by Mizusawa Chemical Industry Co., Ltd., structure: porous)
・Material (B-8): Silica (product name: SO-E2, manufactured by Admatechs Company Limited, structure: spherical)

(Comparative Examples 1 to 3)
Toners 17 to 19 were prepared in the same manner as in Example 1, except that the materials in <Preparation of toner base particles> in Example 1 were changed to the materials shown in Tables 1 to 2 above and the combinations shown in Table 3 below. , Developers 17 to 19, and Images 17 to 19 T-shirts were obtained.
In the same manner as in Example 1, the area average ratio and the average particle diameter of the silica particles were measured and shown in Table 5.

Table 4 below shows the content of each material in the toners obtained in Examples 1 to 16 and Comparative Examples 1 to 3, converted into mass %. In addition, "PEs" in the table indicates polyester.

[Evaluation of washing fastness]
The obtained images 1 to 19 T-shirts were conducted in accordance with Washing Fastness Test (JIS L 0844) No. A-1, and the evaluation was not based on grayscale judgment, but by observing the peeling state of the images before and after the test. and evaluated based on the following evaluation criteria. The results are shown in Table 5.
-Evaluation criteria-
◎: No peeling or cracking, comparable to before evaluation 〇: No major peeling or cracking, but some small peeling spots or cracks (up to 3 places)
△: There are cracks on the image surface, but there are no practical problems. ×: There are noticeable peeling and cracks on the image surface, resulting in missing images and streaks.

[Evaluation of heat-resistant storage stability]
20 g of the obtained toners 1 to 19 were placed in a 100 mL container and stored with the lid open in an environment of 40° C. and 70 RH% for 2 weeks, after which the amount of aggregates generated was measured. To measure the amount of aggregates generated, take the entire amount of toner after storage on a sieve with 106 μm openings, apply vibrations with an amplitude of 1 mm using a vibrator for 1 minute, then measure the amount of toner remaining on the sieve, and perform the following procedure. Evaluation was made based on evaluation criteria. The heat-resistant storage stability of the toner was evaluated based on the amount of aggregates generated. Evaluation was made based on the following evaluation criteria. The results are shown in Table 5.
(Evaluation criteria)
◎: The amount of aggregates remaining on the sieve is less than 1 mg. ○: The amount of aggregates remaining on the sieve is 1 mg or more and less than 2 mg. △: The amount of aggregates remaining on the sieve is 2 mg or more and less than 4 mg. ×: The amount of aggregates remaining on the sieve is 2 mg or more and less than 4 mg. The amount of aggregates remaining in the

From Table 5, it was confirmed that the toners of Examples 1 to 16 met the conditions for use in both washing fastness and heat-resistant storage stability. On the other hand, the toner obtained in Comparative Example 1 did not satisfy the usage conditions in terms of washing fastness, and the toners obtained in Comparative Examples 2 and 3 did not meet the usage conditions in at least the heat-resistant storage property. It was confirmed that there was a problem in practical use.

Although the embodiments have been described as above, the embodiments are presented as examples, and the present invention is not limited to the embodiments described above. The embodiments described above can be implemented in various other forms, and various combinations, omissions, substitutions, changes, etc. can be made without departing from the gist of the invention. These embodiments and their modifications are included within the scope and gist of the invention, as well as within the scope of the invention described in the claims and its equivalents.

Examples of aspects of the present invention are as follows.
<1> A toner comprising a maleic acid-modified polyolefin having at least a polypropylene block in the main chain and silica particles, wherein the content of the maleic acid-modified polyolefin is based on the mass of the toner excluding the colorant. The toner is characterized in that the content is 5% by mass or more and 25% by mass or less, the silica particles are present inside the toner, and the average particle diameter of the silica particles is larger than 1 μm.
<2> The toner according to <1>, which has a sea-island structure containing the maleic acid-modified polyolefin as a domain.
<3> The melting point of the maleic acid-modified polyolefin is 60°C or more and 100°C or less, and the weight average molecular weight of the maleic acid-modified polyolefin is 60,000 or more and 100,000 or less, <1> to <2>. The toner according to any one of the above.
<4> The content of the silica particles is 5% by mass or more based on the mass of the toner excluding the colorant, and the average particle diameter of the silica particles is 1 μm or more and 5 μm or less, <1> The toner according to any one of <3>.
<5> In the toner observed by cross-sectional observation, the number of toner containing silica particles with an average particle diameter of 1 μm or more and 5 μm or less is 60% or more of the total number of toner observed in the toner cross-section. The toner according to any one of <1> to <4>.
<6> The toner according to any one of <1> to <5>, wherein the silica particles have a pore structure or are porous.
<7> The toner according to any one of <1> to <6>, wherein the toner is colorless or white.
<8> A toner set comprising a color toner containing a binder resin and a colorant, and the toner according to any one of <1> to <7>.
<9> A toner storage unit that stores the toner according to any one of <1> to <7>.
<10> An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, a developing step of developing the electrostatic latent image to form a toner image, and transferring the toner image to a recording medium. An image forming method comprising: a transfer step of transferring the toner image to the recording medium; and a fixing step of fixing the transferred image transferred to the recording medium, wherein the toner image is a toner image according to any one of <1> to <7>. This is an image forming method characterized by forming an image using toner.
<11> The image forming method according to <10>, wherein the toner image is formed closer to the recording medium than the color toner image formed by the color toner.

The toner according to any one of <1> to <7>, the toner set according to <8>, the toner storage unit according to <9>, or any one of <10> to <11>. According to the image forming method described in , it is possible to solve the conventional problems and achieve the object of the present invention.

1 Paper feed cassette 2 Paper feed roller 3, 4 Registration roller 4Y, 4C, 4M, 4K Photoreceptor drum 5, 11, 17, 23, 29 Photoreceptor 6, 12, 18, 24, 30 Charger 9, 14, 20 , 26, 32 Developing means 10, 16, 22, 28, 34 Transfer device 8, 15, 21, 27, 33 Cleaning device 7, 13, 19, 25, 31 Exposure light 20Y, 20C, 20M, 20K Toner image forming section 35, 36, 37, 38, 39 Developing unit 30 Cleaning device 40 Charging device 41 Transfer device 43 Fixing device 50 Developing device 60 Intermediate transfer belt 61Y, 61C, 61M, 61K Primary transfer roller 65 Secondary transfer device 70 Paper feed section 71 Paper feed cassette 72 Paper feed roller 73 Registration roller 90 Fixing device

Japanese Patent Application Publication No. 2005-120367 Japanese Patent Application Publication No. 2020-016689 Japanese Patent Application Publication No. 2002-287405

Claims (11)

A toner comprising a maleic acid-modified polyolefin having at least a polypropylene block in the main chain and silica particles,
The content of the maleic acid-modified polyolefin is 5% by mass or more and 25% by mass or less based on the mass of the toner excluding the colorant,
the silica particles are present inside the toner;
A toner characterized in that the average particle diameter of the silica particles is larger than 1 μm. The toner according to claim 1, having a sea-island structure containing the maleic acid-modified polyolefin as a domain. The maleic acid-modified polyolefin has a melting point of 60°C or more and 100°C or less,
The toner according to claim 1, wherein the maleic acid-modified polyolefin has a weight average molecular weight of 60,000 or more and 100,000 or less. The content of the silica particles is 5% by mass or more based on the mass of the toner excluding the colorant,
The toner according to claim 1, wherein the silica particles have an average particle diameter of 1 μm or more and 5 μm or less. In the toner observed by cross-sectional observation, the number of toner containing silica particles having an average particle diameter of 1 μm or more and 5 μm or less is 60% or more of the total number of toner observed in the toner cross-section. The toner according to any one of Items 1 to 2. The toner according to claim 1 , wherein the silica particles have a pore structure or are porous. The toner according to claim 1 , wherein the toner is colorless or white. A toner set comprising: a color toner containing a binder resin and a colorant; and the toner according to claim 1. A toner storage unit that stores the toner according to any one of claims 1 to 2. An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, a developing step of developing the electrostatic latent image to form a toner image, and transferring the toner image to a recording medium. An image forming method comprising a transfer step and a fixing step of fixing the transferred image transferred to the recording medium,
An image forming method, wherein the toner image is formed using the toner according to any one of claims 1 to 2. The image forming method according to claim 10, wherein the toner image is formed closer to the recording medium than the color toner image formed by the color toner.

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