JP2020177063A - toner - Google Patents

Abstract

To provide a toner which offers improvement in terms of scratchability and nail scratchability.SOLUTION: A toner comprising toner particles containing an amorphous polyester resin and a crystalline polyester resin is provided, where the amorphous polyester resin contains a polycondensation product between an ethylene oxide adduct of bisphenol and a tetra- or higher-valent aliphatic carboxylic acid, and the crystalline polyester resin has an SP value of 12.06 or less.SELECTED DRAWING: None

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and toner jet methods.

In recent years, electrophotographic full-color copiers have become widespread and have begun to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are required while supporting a wide range of media (paper types). For example, even if the paper type is changed from thick paper to thin paper, continuous printing is required without changing the process speed or the heating set temperature of the fuser according to the paper type. From the viewpoint of media constant velocity, toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature. Various toners have been proposed in which a crystalline resin having a sharp melt property is added to the toner to improve the low temperature fixing performance in order to fix the toner at a wide range of fixable temperatures (Patent Document 1).

However, even if the image is fixed at 100% image density, toner transfer due to rubbing may occur at a low image density (hereinafter, also referred to as scratchability), and simple low-temperature fixability alone cannot improve the effect. A case has come up. Further, even when the image density is 100%, the toner may be peeled off from the paper when scratched with a sharp tip such as a nail or a ballpoint pen (hereinafter, also referred to as nail scratching property), which is high. From the viewpoint of image quality, there is room for consideration regarding these scratching properties and nail scratching properties.

Japanese Unexamined Patent Publication No. 2012-063559

An object of the present invention is to provide a toner capable of solving the above-mentioned problems and improving scratchability and nail scratchability.

According to the present invention, the toner has toner particles containing an amorphous polyester resin and a crystalline polyester resin.
The amorphous polyester resin
It contains a polycondensation polymer of ethylene oxide adduct of bisphenol and an aliphatic carboxylic acid of tetravalent or higher.
As the crystalline polyester resin, a toner having an SP value of 12.06 or less is provided.

According to the present invention, it is possible to provide a toner capable of solving the above-mentioned problems and improving scratchability and nail scratchability.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
Hereinafter, embodiments for carrying out the present invention will be described in detail.

The toner according to the present invention is
A toner having toner particles containing an amorphous polyester resin and a crystalline polyester resin.
The amorphous polyester resin
It contains a polycondensation polymer of ethylene oxide adduct of bisphenol and an aliphatic carboxylic acid of tetravalent or higher.
The crystalline polyester resin has an SP value of 12.06 or less.
According to the present invention, it is possible to provide a toner capable of improving scratchability and nail scratchability.

Although the reason for solving the above problems in the present invention is not always clear, the present inventors speculate as follows.
Toners using an amorphous polyester resin having an ethylene oxide adduct that does not contain an aliphatic carboxylic acid having a valence of 4 or more and a crystalline polyester resin having an SP value of 12.06 or less are crystalline with the amorphous polyester resin. The SP value is different from that of the polyester resin. Therefore, it is considered that the amorphous polyester resin and the crystalline polyester resin are present in the toner in an incompatible state.

When this toner is fixed on paper, the incompatible crystalline polyester resin melts and exudes to form a crystal layer on the surface of the image. Crystalline polymers generally have bent structures that overlap to form a lamellar structure. The lamellar structure is a layered structure formed by crystallization of a molecular chain of a crystalline polymer by folding. In the lamellar structure, since the lamellars are in contact with each other with a weak intermolecular force, it is considered that the external force can be relaxed between the lamellars. Therefore, it is considered that the lamellar structure forms a layer on the surface of the image to cancel the rubbing force and improve the scraping property.

On the other hand, the strength of the interface between the amorphous polyester resin and the crystalline polyester resin, which is incompatible, is weak, and when scratched with a sharp object, the toner layer on the paper is easily cracked at the interface, and the nails We believe that the scratchability will decrease. By using an amorphous polyester resin having a tetravalent or higher aliphatic carboxylic acid, the crystalline polyester resin and the aliphatic carboxylic acid portion in the amorphous polyester resin interact with each other, and the amorphous polyester resin and the crystalline polyester resin are crystalline. The interface with the polyester resin is strengthened. As a result, it is considered that it is possible to provide a toner that improves the nail scraping property while maintaining good scratching property.

The composition of the toner for achieving the object in the present invention will be described in detail below.
As the binding resin, a polyester resin having a "polyester unit" in the binding resin chain is used. As a component constituting the polyester unit, it is necessary to contain at least an ethylene oxide adduct of bisphenol and an aliphatic carboxylic acid having a valence of 4 or more.

The ratio of the ethylene oxide adduct of bisphenol in the polyhydric alcohol monomer constituting the amorphous polyester resin is 60 mol% or more with respect to the total number of moles of the polyhydric alcohol monomer, which makes the crystalline polyester more non-phase. It is preferable from the viewpoint of scratchability because it can exist in a molten state.

For example, examples of the tetravalent or higher valent aliphatic carboxylic acid include the following.
1,1,2,2-ethanetetracarboxylic acid, 1,1,1,2-ethanetetracarboxylic acid, 1,1,3,3-polypantetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid Carboxylic acid, 1,1,2,2-propanetetracarboxylic acid, 2- (carboxymethyl) propane-1,1,3-tricarboxylic acid, 1,1,4,4-butanetetracarboxylic acid, 1,1, 2,4-Butantetracarboxylic acid, 1,1,3,4-butanetetracarboxylic acid, 1,1,2,2-butanetetracarboxylic acid, 1,1,3,3-butanetetracarboxylic acid, 2, 2,3,3-butanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,1,5,5-pentanetetracarboxylic acid, 1,1,4,5-pentanetetracarboxylic acid, 1,1,3,5-pentanetetracarboxylic acid, 1,1,2,5-pentanetetracarboxylic acid, 1,1,4,4-pentanetetracarboxylic acid, 1,1,3,4-pentanetetracarboxylic acid Acid, 1,1,2,4-pentanetetracarboxylic acid, 1,1,3,3-pentanetetracarboxylic acid, 1,1,2,3-pentanetetracarboxylic acid, 1,1,2,2-pentane Tetracarboxylic acid, 1,2,3,4-pentanetetracarboxylic acid, 1,2,3,5-pentanetetracarboxylic acid, 3- (carboxymethyl) butane-1,1,4-tricarboxylic acid, 2-( Carboxymethyl) butane-1,1,4-tricarboxylic acid, 2-methylbutane-1,1,4,4-tetracarboxylic acid, 1,1,6,6-hexanetetracarboxylic acid, 1,1,5,6 -Hexanetetracarboxylic acid, 1,2,3,4-hexanetetracarboxylic acid, 1,2,3,5-hexanetetracarboxylic acid, 1,2,3,6-hexanetetracarboxylic acid, 2-methylpentane- 1,1,5,5-tetracarboxylic acid, 3-methylpentane-1,1,5,5-tetracarboxylic acid, 2,3-dimethylbutane-1,1,4,4-tetracarboxylic acid, 1, 1,7,7-Heptanetetracarboxylic acid, 1,1,8,8-octanetetracarboxylic acid, 1,1,9,9-nonanetetracarboxylic acid, 1,1,10,10-decanetetracarboxylic acid, 3,5-Bis (carboxymethyl) -3,4,5,5-tetramethylheptandiic acid and the like.

As other constituents, an arbitrary divalent or higher alcohol monomer component and an acid monomer component such as a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, and a divalent or higher carboxylic acid ester are used. Can be done.
For example, the following are examples of the divalent or higher valent alcohol monomer component.
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adduct of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1 , 4-Butanediol, Neopentyl glycol, 1,4-Butenediol, 1,5-Pentanediol, 1,6-hexanediol, 1,4-Cyclohexanedimethanol, Dipropylene glycol, Polyethylene glycol, Polypropylene glycol, Poly Tetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5- Pentaerythritol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

On the other hand, examples of the acid monomer component such as the divalent or higher carboxylic acid, the divalent or higher carboxylic acid anhydride and the divalent or higher carboxylic acid ester include the following.
Aromatic dicarboxylic acids or anhydrides thereof such as phthalic acid, isophthalic acid and terephthalic acid; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; alkyl groups having 6 to 18 carbon atoms. Alternatively, succinic acid or an anhydride thereof substituted with an alkenyl group; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

The amorphous polyester resin preferably has a weight average molecular weight (Mw) of 5,000 or less from the viewpoint of nail scraping property.

The amorphous polyester resin preferably has a glass transition temperature (Tg) of 58 ° C. or higher and 65 ° C. or lower from the viewpoint of nail scraping property.

The acid value of the amorphous polyester resin is preferably 0 mgKOH / g or more and 50 mgKOH / g or less from the viewpoint of obtaining excellent charge stability, and more preferably 1 mgKOH / g or more and 20 mgKOH / g or less.
The acid value can be set in the above range by adjusting the type and blending amount of the monomer used in the resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and the molecular weight at the time of resin production. Further, it can be controlled by reacting the terminal alcohol with a polyhydric acid monomer (for example, trimellitic acid) after ester polycondensation.
The softening point of these binder resins is preferably 70 ° C. or higher and 180 ° C. or lower, and more preferably 80 ° C. or higher and 160 ° C. or lower, from the viewpoint of achieving both low-temperature fixability and hot offset resistance.

[Crystalline polyester resin]
The toner of the present invention needs to contain a crystalline polyester resin having an SP value of 12.06 or less. By containing the crystalline polyester resin, the crystalline polyester resin is incompatible with each other in the toner particles. By fixing the toner particles on the image, the scratch resistance is improved. The compatibility of the crystalline polyester resin can be adjusted by increasing the carbon number of the aliphatic diol and / or the aliphatic dicarboxylic acid of the monomer constituting the crystalline polyester resin, lowering the ester group concentration, and lowering the polarity.

In the present invention, the solubility parameter is calculated by the Fedors method. The evaporation energy (Δei [cal / mol]) and molar volume (Δvi [cm ³ / mol]) used in the calculation are described in Chapter 5, R.M., published by Minoru Inoue, "Basic Theory of Adhesion". F. Fedors, Polym. Eng. Sci. The numerical values described in 14, 147 (1974) are used. In the present invention, the calculation is performed based on the structure of the polymer constituent unit.

In the toner of the present invention, the crystalline polyester contained in the toner particles can be obtained by polycondensing a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid as main components. The aliphatic diol and the aliphatic dicarboxylic acid preferably have 6 to 12 carbon atoms.

The aliphatic diol is not particularly limited as long as the SP value of the obtained crystalline polyester resin is 12.06 or less, but it is preferably a chain-like (more preferably linear) aliphatic diol. For example, the following can be mentioned.
1,4-Butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol Neopentyl glycol. Of the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from an aliphatic diol having 6 to 12 carbon atoms.

In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A; 1,4-cyclohexanedimethanol and the like. In addition, examples of the trihydric or higher polyhydric alcohol monomer among the polyhydric alcohol monomers include the following.
Aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-pentanetriol, glycerin, 2-methyl Aliper alcohols such as propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

On the other hand, the aliphatic dicarboxylic acid is not particularly limited as long as the SP value of the obtained crystalline polyester resin is 12.06 or less, but is not particularly limited, but is a chain (more preferably linear) aliphatic dicarboxylic acid. Is preferable. Specific examples include the following.
Adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid. Hydrolyzed amounts of these acid anhydrides or lower alkyl esters are also included.
In the present invention, preferably 50% by mass or more, more preferably 70% by mass or more of the carboxylic acid components are carboxylic acids selected from aliphatic dicarboxylic acids having 6 to 12 carbon atoms.

In the present invention, polyvalent carboxylic acids other than aliphatic dicarboxylic acids can also be used. Among the other polyvalent carboxylic acid monomers, examples of the divalent carboxylic acid include the following.
Aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids of n-dodecylsuccinic acid and n-dodecenylsuccinic acid; alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These acid anhydrides or lower alkyl esters are also included.

Among other carboxylic acid monomers, examples of trivalent or higher valent carboxylic acids include the following.
Aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid. Aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane. Derivatives such as these acid anhydrides or lower alkyl esters are also included.

The crystalline polyester in the present invention can be produced according to a conventional polyester synthesis method. For example, it is desired to carry out an esterification reaction or a transesterification reaction between the carboxylic acid monomer and the alcohol monomer described above, and then carry out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Crystalline polyester can be obtained.

The esterification or transesterification reaction can be carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate, if necessary.
Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. .. The polymerization temperature and the amount of catalyst are not particularly limited and may be appropriately determined.

In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be mixed together in order to increase the strength of the obtained crystalline polyester. Further, in order to reduce the low molecular weight component, a method such as first reacting a divalent monomer and then adding a trivalent or higher valent monomer to react may be used.

The crystalline polyester is preferably contained in an amount of 1.0 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the amorphous resin. If the amount of the crystalline resin is small, the scratching effect cannot be sufficiently obtained, and if it is added too much, the interface between the crystalline polyester and the amorphous polyester increases, and the nail scratching property is lowered.

[wax]
The toner of the present invention may contain a wax, and examples of the wax used in the toner of the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; Waxes containing fatty acid esters such as carnauba wax as the main component; deoxidized fatty acid esters such as carnauba wax partially or wholly deoxidized. Among these waxes, hydrocarbon waxes such as paraffin wax and Fishertroph wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low temperature fixability and hot offset resistance.

In the present invention, a hydrocarbon-based wax or an ester-based wax is more preferable in that it has low-temperature fixability and further improves hot offset resistance. The content of the wax is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin. When the wax content is in this range, it tends to be possible to exert the effect of maintaining the hot offset property at a high temperature.

Further, from the viewpoint of achieving both toner storage stability and high temperature offset property, the maximum endothermic heat existing in the temperature range of 30 ° C. or higher and 200 ° C. or lower in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry apparatus (DSC). The peak temperature of the peak is preferably 50 ° C. or higher and 140 ° C. or lower. More preferably, it is 60 ° C. or higher and 105 ° C. or lower.

[Colorant]
Examples of the colorant that can be contained in the toner of the present invention include the following.
Examples of the black colorant include carbon black; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. A pigment may be used alone as the colorant, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.

Examples of the magenta toner pigment include the following. C. I. Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,22,23,24,27,29,32,34,35,36,37,38,39,40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine methyl groups are substituted in the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. There is Solvent Blue 70.

Examples of the pigment for yellow toner include the following. C. I. Pigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,62,65,73,74,83,93,94,95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.
Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.

[Charge control material]
The toner of the present invention may also contain a charge control agent, if necessary. Examples of the charge control agent include the following as negative charge control agents. A polymer compound having a metal salicylate compound, a metal naphthoate compound, a metal dicarboxylic acid compound, a sulfonic acid or a carboxylic acid in a side chain. A polymer compound having a sulfonate or a sulfonic acid esterified product in the side chain. A polymer compound having a carboxylate or a carboxylic acid esterified product in the side chain. Boron compounds, urea compounds, silicon compounds, calixarene. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added is preferably 0.1 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Other external additives]
The toner of the present invention may contain other inorganic fine powders, if necessary. The inorganic fine powder may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powder such as silica, titanium oxide, and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As the external additive for improving the fluidity, an inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable, and for stabilizing durability, the specific surface area is 10 m ² / g or more and 50 m. It is preferably an inorganic fine powder of ² / g or less. In order to improve the fluidity and stabilize the durability, an inorganic fine powder having a specific surface area in the above range may be used in combination.
The external additive is preferably used in an amount of 0.1 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

[Career]
The toner of the present invention can also be used as a one-component developer, but in order to further improve dot reproducibility, a two-component developer mixed with a magnetic carrier can be obtained in a stable image for a long period of time. It is more preferable to use as.
Examples of the magnetic carrier include iron powder whose surface has been oxidized, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth, and alloys thereof. Generally known, such as a magnetic material such as particles, oxide particles, and ferrite, or a magnetic material-dispersed resin carrier (so-called resin carrier) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state. You can use things.
When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the two-component developer. Is 4% by mass or more and 13% by mass or less. When the toner concentration in the two-component developer is set to such a range, good results are usually obtained.

[Production method]
The toner particles of the present invention can be produced by conventionally known toner production methods such as an emulsion aggregation method, a melt-kneading method, and a dissolution-suspension method, and are not particularly limited.
If necessary, an external additive selected may be added to the toner particles produced by the above-mentioned production method and mixed (externally added). Examples thereof include inorganic fine powders such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester resin and silicone resin. These inorganic fine powders and resin particles function as external additives such as charge control, fluidity aid, and cleaning aid. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries Co., Ltd.) and the like.
Next, a method for measuring each physical property related to the present invention will be described.

[Measurement of weight average particle size (D4) of toner particles]
The weight average particle size (D4) of the toner particles is the same as that of the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electric resistance method. , Measured with 25,000 effective measurement channels using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter Co., Ltd.) for setting measurement conditions and analyzing measurement data. Then, the measurement data is analyzed and calculated.

As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in deionized water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. ..
Before performing measurement and analysis, the dedicated software is set as follows.

In the "Standard measurement method (SOM) change screen" of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is once, and the Kd value is "Standard particle 10.0 μm" (Beckman). -Set the value obtained using Coulter Co., Ltd. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows (1) to (7).

(1) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the "aperture flash" function of the analysis software removes dirt and air bubbles in the aperture tube.
(2) Put about 30 mL of the electrolytic aqueous solution in a 100 mL flat-bottomed beaker made of glass, and add about 0.3 mL of a diluted solution prepared by diluting the following "contamination N" with deionized water 3 times by mass as a dispersant. ..
Contaminone N: 10% by mass aqueous solution of neutral detergent for cleaning a precision measuring instrument with pH 7 consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.

(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and the water tank of the ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of deionized water is put therein, and about 2 mL of the contaminanton N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.

(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped into the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. To do. Then, the measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

[Measurement method of average circularity]
The average circularity of the toner particles is measured by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.
The specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. ) Is diluted with ion-exchanged water about 3 times by mass, and about 0.2 mL of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion liquid is appropriately cooled so that the temperature is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervocreer Co., Ltd.)) having an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount is contained in the water tank. Ion-exchanged water of No. 1 is put in, and about 2 mL of the Contaminone N is added into this water tank.

The flow-type particle image analyzer equipped with a standard objective lens (10 times) was used for the measurement, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3,000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold value at the time of particle analysis is set to 85%, the diameter of the analyzed particle is limited to 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

In the measurement, automatic focus adjustment is performed using the following standard latex particles before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.
-Standard latex particles: "RESAARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific diluted with ion-exchanged water.

In the embodiment of the present application, a flow-type particle image analyzer that has been calibrated by Sysmex Corporation and has received a calibration certificate issued by Sysmex Corporation was used. The measurement was performed under the same measurement and analysis conditions as when the calibration certificate was obtained, except that the diameter of the analysis particle was limited to 1.985 μm or more and less than 39.69 μm in equivalent circle diameter.

[Measuring method of softening point Tm of binder resin]
The softening point of the binder resin is measured by using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) and following the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. A flow curve showing the relationship between and temperature can be obtained.

Further, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

The measurement sample is about 1.0 g of resin compressed and molded in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. However, a columnar one having a diameter of about 8 mm is used.
The measurement conditions for the CFT-500D are as follows.
Test mode: Hot compress start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise rate: 4.0 ° C / min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

[Measurement of acid value of resin]
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide gas or the like, allow it to stand for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As for the factor of the potassium hydroxide solution, 25 mL of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.

(2) Operation (A) Main test 2.0 g of the sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: sample (g).

[Measurement of molecular weight of crystalline resin by GPC]
First, the crystalline resin is dissolved in o-dichlorobenzene at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-H HT 7.8 cm I. D x 30 cm ² stations (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135 ° C
Solvent: o-dichlorobenzene (with 0.05% ionol added)
Flow velocity: 1.0 mL / min
Sample: Inject 0.4 mL of 0.1% sample. Measure under the above conditions, and use the molecular weight calibration curve prepared from the monodisperse polystyrene standard sample to calculate the molecular weight of the sample. Further, it is calculated by converting to polyethylene by a conversion formula derived from the Mark-Houwink viscosity formula.

[Measurement of molecular weight of amorphous resin by GPC]
The molecular weight distribution of the THF-soluble component of the resin is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

In calculating the molecular weight of the sample, for example, a molecular weight calibration curve prepared using the following standard polystyrene resin manufactured by Tosoh Corporation is used.
Standard polystyrene resin: Product name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "

[Measurement of glass transition temperature (Tg) of amorphous resin and toner]
[Measurement of melting peak temperature (Tp) of crystalline resin]
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 3 mg of resin or toner is precisely weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference.
Temperature rise rate: 10 ° C / min
Measurement start temperature: 30 ° C
Measurement end temperature: 180 ° C

The measurement is performed at a heating rate of 10 ° C./min in the measurement range of 30 to 180 ° C. The temperature is once raised to 180 ° C. and held for 10 minutes, then lowered to 30 ° C., and then the temperature is raised again. In this second heating process, a change in specific heat is obtained in the temperature range of 30 to 100 ° C. At this time, the temperature at the intersection of the straight line at the same distance in the vertical axis direction from the "baseline before the specific heat change" and the "baseline after the specific heat change" and the differential thermal curve is set to the temperature of the resin. It is defined as the glass transition temperature (Tg, also referred to as the intermediate point glass transition temperature). Further, the temperature at which the maximum endothermic peak of the temperature-endothermic amount curve in the temperature range of 60 to 90 ° C. is defined as the melting peak temperature (Tp).

Hereinafter, the present invention will be described with reference to Production Examples and Examples. In the following description, the number of copies is based on parts by mass.
<Production example of binder resin>
(Production example of amorphous polyester resin A1)
-Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane:
29.7 parts by mass (0.07 mol; 40.0 mol% with respect to the total number of moles of polyhydric alcohol)
-Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane:
40.8 parts by mass (0.13 mol; 60.0 mol% with respect to the total number of moles of polyhydric alcohol)
-Terephthalic acid: 30.4 parts by mass (0.195 mol; 97.5 mol% based on the total number of moles of polyvalent carboxylic acid)
D1 3,5-bis (carboxymethyl) -3,4,5,5-tetramethylheptanedioic acid: 1.66 parts by mass (0.005 mol; 2.4 mol with respect to the total number of moles of polyvalent carboxylic acid %)

The above materials were put into a cooling pipe, a stirrer, a nitrogen introduction pipe, and a reaction vessel equipped with a thermocouple. Then, 1.0 part by mass of tin 2-ethylhexanoate (esterification catalyst) was added as a catalyst to 100 parts by mass of the total amount of the monomers. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2.5 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180 ° C., and returned to atmospheric pressure (first reaction step).
Trimellitic anhydride: 0.04 parts by mass (0.0002 mol; 0.1 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 part After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160 ° C., ASTM D36- After confirming that the softening point of the reaction product measured according to 86 reached 140 ° C., the temperature was lowered to stop the reaction (second reaction step). In this way, the amorphous polyester resin A1 was obtained. The obtained amorphous polyester resin A1 had a softening point (Tm) of 98 ° C. and an acid value of 10 mgKOH / g.

<Production example of amorphous polyester resins A2 to A12>
In the production example of the amorphous polyester resin A1, the same was produced except that the types and amounts of the polyhydric alcohol monomer and the polyvalent carboxylic acid monomer were changed to those shown in Table 1A, and the amorphous polyester resins A2 to I got A12. The physical properties of the obtained amorphous polyester resin are shown in Table 1A.

<Production example of crystalline polyester resin C1>
・ 1,12-Dodecanediol:
58.7 parts by mass (0.29 mol; 100.0 mol% with respect to the total number of moles of polyhydric alcohol)
・ Dodecanedioic acid:
58.7 parts by mass (0.29 mol; 100.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.
Next, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C.
Then, the inside of the reaction vessel was reduced to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain crystalline polyester C1.
The obtained crystalline polyester C1 had a weight average molecular weight (Mw) of 15,000, a softening point (Tm) of 82 ° C., and an SP value of 10.80.

<Production example of crystalline polyester resins C2 to C6>
In the production example of the crystalline polyester resin C1, the same as the crystalline polyester resin C1 was produced except that the types of the dialcohol monomer and the dicarboxylic acid monomer were changed to those shown in Table 1B. The physical properties of the obtained crystalline polyester resins C2 to C6 are shown in Table 1B.

<Manufacturing example of toner 1>
・ Amorphous polyester resin A1 100.0 parts by mass ・ Crystalline polyester resin C1 5.0 parts by mass ・ 3,5-Di-t-Aluminum salicylate compound (CA) 0.1 parts by mass ・ Fisher tropschwax (maximum) Peak temperature of heat absorption peak 90 ° C.) 5.0 parts by mass ・ C.I. I. Pigment Blue 15: 3 9.0 parts by mass

The raw materials shown in the above formulation are mixed using a Henschel mixer (FM75J type, manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 20 s- ¹ and a rotation time of 5 min, and then set at a temperature of 130 ° C. and a barrel rotation speed of 200 rpm. The mixture was kneaded using the following twin-screw kneader.
Biaxial kneader: PCM-30 type, manufactured by Ikegai Co., Ltd. The obtained kneaded product was cooled and roughly pulverized to 1 mm or less with a hammer mill to obtain a coarse crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles 1. The operating conditions of the rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) were that the classifying rotor rotation speed was 50.0 s ^-1 .

The following materials are mixed using a Henschel mixer (FM75J type, manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 30 s- ¹ and a rotation time of 5 min, and passed through an ultrasonic vibrating sieve with a mesh opening of 54 μm to obtain toner 1. It was.
・ Toner particles 1 100.0 parts by mass ・ Hydrophobic silica (BET: 200 m ² / g) 5.0 parts by mass ・ Titanium oxide fine particles surface-treated with isobutylmethoxysilane (BET: 80 m ² / g)
7.0 parts by mass

<Manufacturing example of toners 2 to 16>
In the production example of the toner 1, the toners 2 to 16 were obtained in the same manner except that the types and amounts of the amorphous polyester resin A1 and the crystalline polyester resin C1 were changed to those shown in Table 2.

[Production example of magnetic core particles]
(Step 1: Weighing / mixing process)
・ Fe ₂ O ₃ 62.7 parts by mass ・ MnCO ₃ 29.5 parts by mass ・ Mg (OH) ₂ 6.8 parts by mass ・ SrCO ₃ 1.0 parts by mass Make the above material into the above composition ratio. Weighed. Then, it was pulverized and mixed for 5 hours with a dry vibration mill using stainless beads having a diameter of 1/8 inch.

-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve having an opening of 3 mm, and then fine powder was removed with a vibrating sieve having an opening of 0.5 mm. Then, using a burner type firing furnace, calcining was carried out in a nitrogen atmosphere (oxygen concentration 0.01% by volume) at a temperature of 1,000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393

(Step 3: Crushing step)
After crushing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was pulverized with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

(Step 4: Granulation process)
To 100 parts by mass of calcined ferrite, 1.0 part by mass of ammonium polycarboxylic acid as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to the ferrite slurry. Then, using a spray dryer (manufacturer: Okawara Kakoki Co., Ltd.), the particles were granulated into spherical particles. After adjusting the particle size of the obtained particles, the particles were heated at a temperature of 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.

(Step 5: Baking step)
In order to control the firing atmosphere, the temperature is raised from room temperature to a temperature of 1,300 ° C. in 2 hours under a nitrogen atmosphere (oxygen concentration of 1.00% by volume) in an electric furnace, and then 4 at a temperature of 1,150 ° C. Bake for hours. Then, over 4 hours, the temperature was lowered to 60 ° C., the nitrogen atmosphere was returned to the atmosphere, and the mixture was taken out at a temperature of 40 ° C. or lower.

(Step 6: Sorting step)
After crushing the agglomerated particles, the low magnetic force product is cut by magnetic beneficiation and sieved with a sieve having a mesh size of 250 μm to remove coarse particles. Magnetic core particles having a volume distribution-based median diameter of 37.0 μm 1 (Ferrite particles 1) were obtained.

[Preparation of coating resin]
-Cyclohexyl methacrylate monomer 26.8% by mass
-Methyl methacrylate monomer 0.2% by mass
-Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5,000)
・ Toluene 31.3% by mass
・ Methyl ethyl ketone 31.3% by mass
・ Azobisisobutyronitrile 2.0% by mass

Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer. Then, nitrogen gas was introduced and the inside of the system was replaced with nitrogen gas. Then, the temperature was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration and vacuum dried to obtain a coating resin 1. The obtained coating resin 1 30 parts by mass was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

[Preparation of coating resin solution]
-Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
-Toluene 66.4% by mass
・ Carbon black 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 mL / 100 g)
The above material was dispersed in a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

[Manufacturing example of magnetic carrier]
(Resin coating process)
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the ferrite particles 1. After the addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic carrier was separated into low magnetic force products by magnetic beneficiation, passed through a sieve having an opening of 70 μm, and then classified by a wind power classifier to obtain a magnetic carrier 1 having a volume distribution-based median diameter of 38.2 μm. ..

Rotation speed of the toners 1 to 16 and the magnetic carrier 1 (number average particle size 35 μm) using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner concentration becomes 9% by mass. Mixing was carried out at 0.5 s- ¹ and a rotation time of 5 minutes to obtain two-component developers 1 to 16.

(Toner evaluation)
As an image forming apparatus to be evaluated, a full-color copying machine imagePRESS C800 modified machine manufactured by Canon Inc. was used. This image forming apparatus has a photoconductor that forms an electrostatic latent image as an image carrier, and has a developing step of developing the electrostatic latent image of the photoconductor as a toner image by a two-component developer. Further, it has a transfer step of transferring the developed toner image to an intermediate transfer body and then transferring the toner image of the intermediate transfer body to paper, and has a fixing step of fixing the toner image on paper by heat. The image forming apparatus was modified so that the temperature control and process speed of fixing could be changed. The two-component developer 1 was put into the developing machines of the cyan station and the magenta station of this image forming apparatus and evaluated.

[Scratchability evaluation]
A monochromatic image was formed with the two-component developer 1. At this time, an image was formed by dividing the image from 00h (solid white) to the FFh image (solid part) with 16 gradations. In image formation, the amount of the FFh image (solid part) of the two-component developer 1 was set to the amount of the image density of 0.9 in a single color.
Paper: Oce Top Coated Plus Silk 270g (270.0g / m ² )
Fixation test environment: Room temperature and humidity environment: Temperature 23 ° C / Relative humidity 50%

The process speed was set to 450 mm / sec, the fixing temperature was set to 170 ° C., and the scratch resistance evaluation image was output.
With respect to the obtained 16-gradation secondary color image, the fourth image from the lightest, including solid white, is cut into strips and set upward in the following device. Only paper is set in the damper part, and the rubbing test is carried out under the following conditions.
Rubbing tester: Gakushin new friction fastness tester (AB-301)
Weight: 500g (0.5kgf)
Stroke: 10 round trips

The rubbed paper (rubbing paper) are shifted toner, this rubbing paper and white paper, SpectroScan Transmission (GretagMacbeth Co., _Ltd.): the gradation of the image using (measurement condition _{D 50} viewing angle 2 °) L ^* , A ^* , and b ^* were measured.
ΔE = {(L ₁ ^* ) ² + (a ₁ ^* ) ² + (b ₁ ^* ) ² } ^0.5 ― {(L ₂ ^* ) ² + (a ₂ ^* ) ² + (b ₂ ^* ) ² } A ΔE of ^0.5 was compared and used as an index for evaluating scratchability.
L ₁ ^* : Rubbed paper L ^* , a ₁ ^* : Rubbed paper a ^* , b ₁ ^* : Rubbed paper b ^*
L ₂ ^* : Blank L ^* , a ₂ ^* : Blank a ^* , b ₂ ^* : Blank b ^*
(Evaluation criteria)
A: ΔE is less than 2.0 (very good)
B: ΔE is 2.0 or more and less than 5.0 (good)
C: ΔE is 5.0 or more and less than 10.0 (a level that is not a problem in the present invention)
D: ΔE is 10.0 or more (not acceptable in the present invention)

[Nail scratching]
A monochromatic, solid image was formed with the two-component developer 1. At this time, the loading amount was set so that the image density of the solid portion was 1.80.
Paper: SPLENDLUX 135g (135.0g / m ² )
The process speed was set to 450 mm / sec, the fixing temperature was set to 170 ° C., and a nail scratching property evaluation image was output.
All the obtained solid images are cut into strips and a scratch test is carried out under the following conditions.
Scratch tester: Surface quality measuring instrument TYPE: 14
Needle: 0.75 mm in diameter
SPEED: 0060mm / min
SCALE: 030mm
FORCE: 0.98
Load: 20g

The part where the image is peeled off by scratching is white. The area ratio of the white part (white area ratio) is calculated using the image processing software ImageJ (developer Wayne Rashand).
The area ratio was calculated as follows.
First, the scratched sample is scanned and opened with ImageJ.
Next, from Color of the Image tab, SplitChannels is performed and divided into RGB.
Next, from the images divided into RGB, the image in which the white spots are most conspicuous is selected.
Next, with the selected image, perform Threhold from Adjust on the Image tab, adjust so that the white spots are selected in red, and apply.
Next, an analysis range of 64 × 1023 is set, and the white spots are included in the analysis range.

Next, select the Analysis Particle on the Analysis tab, check the Summerize, and select OK.
Next, the value of Area Fraction of the Summery window was read, and the value was calculated as the whiteout area ratio.
Subsequently, the load is changed to 50 g, 70 g, 100 g, and 150 g, and the whiteout area ratio is calculated in the same manner using the image processing software ImageJ (developed by Wayne Rashand). From the approximate formula of the white spot area ratio calculated with respect to the load, the load at which the image begins to peel off (the load at which the white spot area ratio is 0.2% or more. Also referred to as the white spot load) is obtained, and the claw is scraped. It was used as an index for sexual evaluation.

(Evaluation criteria)
A: Whiteout load is 150g or more (very excellent)
B: Whiteout load is 100g or more and less than 150g (good)
C: Whiteout load is 50 g or more and less than 100 g (the level is not a problem in the present invention).
D: Whiteout load is less than 50 g (not acceptable in the present invention)
The evaluation results are shown in Table 3.

二成分系現像剤２〜１６についても二成分系現像剤１と同様の評価を行った。結果を表３に示す。

The two-component developer 2 to 16 were also evaluated in the same manner as the two-component developer 1. The results are shown in Table 3.

Claims (6)

A toner having toner particles containing an amorphous polyester resin and a crystalline polyester resin.
The amorphous polyester resin
It contains a polycondensation polymer of ethylene oxide adduct of bisphenol and an aliphatic carboxylic acid of tetravalent or higher.
The crystalline polyester resin is a toner having an SP value of 12.06 or less. The toner according to claim 1, wherein the ratio of the ethylene oxide adduct of bisphenol in the polyhydric alcohol monomer constituting the amorphous polyester resin is 60 mol% or more with respect to the total number of moles of the polyhydric alcohol monomer. The toner according to claim 1 or 2, wherein the amorphous polyester resin has a weight average molecular weight (Mw) of 5,000 or less. The toner according to any one of claims 1 to 3, wherein the amorphous polyester resin has a glass transition temperature (Tg) of 58 ° C. or higher and 65 ° C. or lower. The toner according to any one of claims 1 to 4, wherein the amorphous polyester resin has an acid value of 1 mgKOH / g or more and 20 mgKOH / g or less. The toner according to any one of claims 1 to 5, wherein the tetravalent or higher aliphatic carboxylic acid is 3,5-bis (carboxymethyl) -3,4,5,5-tetramethylheptanedioic acid. ..