Resin particle, toner, developer, developer container, method for producing resin particles, method for producing toner, image forming apparatus and image forming method (2023)

This patent application is based on and claims the priority of 35 U SC. §119(a) of Japanese Patent Application No. 2021-177996 and No. 2022-026855 filed with the Japan Patent Office on October 29, 2021 and February 24, 2022, respectively, the information of which is incorporated here for reference.

The present invention relates to resin particles, toner, developer, developer container, resin particle producing method, toner producing method, image forming apparatus and image forming method.

Carbon neutral is a term commonly used to define biomass materials, including organic matter. When these biomass materials are burned, carbon dioxide is emitted. The carbon dioxide contained in carbon dioxide originates from carbon dioxide absorbed from the atmosphere by photosynthesis during the growth of biomass materials. Therefore, all things considered, the use of biomass materials will not increase the amount of carbon dioxide in the atmosphere. This property is known as carbon neutrality.

Conventionally, toner components, especially binder resins, are basically dependent on fossil resources, and carbon dioxide generated by toner disposal and image printing is considered to be released into the atmosphere, e.g. causing pollution. global warming. Furthermore, it can also be said that the conversion of fossil resources, which are renewable resources, to biomass resources, which are renewable resources, is a conversion to sustainable renewable resources from the point of view of generating living organisms using solar energy, water and carbon. dioxide. This technique is very popular.

Examples of toner components obtained from such renewable resources include, but are not limited to, release agents such as carnauba wax and candelilla wax. These release agents are mixed with the toner to provide a release function for setting. Since the mixing amount of the mold release agent is generally about a few percent by weight, this amount is far from satisfying carbon neutrality.

In recent years, energy consumption has grown in line with population growth, and as resources are depleted, the need for e.g. More and more attention has been paid to the conservation of energy and resources, to the recycling of resources. Local authorities have recycled the polyethylene terephthalate (PET) bottles and used them in various types of clothing and containers. In addition, there is a great demand for the development of new applications that allow the reuse of recycled PET. From this point of view, toner binder resins are produced as raw materials from recycled polyethylene terephthalate, and toners (recycled toners) containing these toner binder resins are known.

Today, there is a strong demand for toners to use biomass-derived resins to improve toner functions while improving environmental adaptability.

One embodiment of the present invention provides a resin particle that includes a binder resin. Binder resins include resins derived from biomass and recycled resins. The content (mass %) of the biomass-derived resin and the content (mass %) of the recycled resin in the binder resin satisfy the following relational expression (1).

Recycled resin content > Biomass-derived resin content(1)

A fuller understanding of the present description and its many attendant features and advantages can be readily obtained and understood from the following detailed description with reference to the accompanying drawings, in which:

As shown in the picture.1is a schematic diagram illustrating an image forming apparatus according to an embodiment of the present invention. and

As shown in the picture.2Fig. 1 is a schematic diagram illustrating a process cartridge in accordance with one embodiment of the present invention.

The drawings are intended to represent embodiments of the invention and are not to be construed as limiting its scope. The drawings will not be considered drawn to scale, unless expressly indicated. In addition, the same or similar reference numerals indicate the same or similar components throughout the various figures.

In describing the embodiments shown in the drawings, specific terminology will be used for clarity. However, the publication of this specification is not intended to be limited to the specific terms so chosen, and each specific element should be understood to include all technical equivalents that perform a similar function, operate in a similar manner, and achieve a similar result. .

Referring now to the drawings, embodiments of the present disclosure will be described below. As used here, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

Embodiments of the present invention provide resin particles suitable for an environmentally friendly toner which are excellent in fixability, storage and durability.

The embodiments of the present invention will be explained in order.

(1) The resin particles according to the embodiment of the present invention contain at least one binder resin. Binder resins include resins derived from biomass and recycled resins. The content (mass %) of the biomass-derived resin and the content (mass %) of the recycled resin in the binder resin satisfy the relational expression (1).

Recycled resin content > Biomass-derived resin content(1)

As the binder resin, polyester resin is preferable. To improve storability and durability, it is preferred that the polyester resin contain bisphenol A propylene oxide (BPA-PC) or bisphenol A ethylene oxide (BPA-EO) as an alcohol component to increase toughness. As biomass conversion progresses, the use of plant-based alcohol components increases and the use of BPA decreases. Lack of use of BPA also reduces the hardness of polyester resin and reduces storability and durability. Therefore, the ratio of "regenerated resin content>biomass-derived resin content" will be met to achieve all fixability, storage, and durability.

(2) In the resin pellet according to (1) above, the total content of the recycled resin and biomass-derived resin in the binder resin is preferably 80% by weight or more.

Content of 80% by mass or more improves environmental adaptability and achieves full fixability, storage, and durability.

(3) In the resin particles described in (1) or (2) above, the recycled resin is preferably at least one of polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

(4) The resin particles described in any of (1) to (3) above preferably contain a polyester resin. The inclusion of polyester resin provides good fixing capacity.

(5) The resin particles according to (4) above preferably contain a crystalline polyester resin as the polyester resin.

The inclusion of a crystalline polyester resin in the resin particles is expected to improve tackability at low temperature.

(6) The resin particles described in any of the above items (1) to (5) preferably further contain a dye and a release agent.

(7) The toner according to the embodiment of the present invention can be produced by adding an external additive to the resin particles according to (6) above.

(8) The toner according to (7) above can be used as a developer in an image forming apparatus.

(9) The developer according to (8) above may be contained in a developer storage container in an image forming apparatus.

(10) The method for producing resin particles according to the embodiment of the present invention includes mixing at least one binder resin and a binder resin precursor. Here, the binder resin comprises at least one biomass-derived resin and one recycled resin, and the content (mass %) of the biomass-derived resin and the content (mass %) of the recycled resin in the binder resin satisfy the following conditions (1).

Recycled resin content > Biomass-derived resin content(1)

(11) The production method of the resin particles described in (10) above may also include:

Step a: dissolving or dispersing at least one of the binder resin and the precursor, optionally together with a dye, in an organic solvent to prepare a solution;

Method b: Water is added to the solution to convert the solution phase from a water-in-oil dispersion to an oil-in-water dispersion:

Step c: removal of the organic solvent from the oil-in-water dispersion to obtain a dispersion of microparticles. and

Step d: Aggregation of the fine particles in the fine particle dispersion to obtain aggregated particles.

By carrying out the above production method, resin particles with improved fixability, storage and durability can be obtained.

(12) In the resin particle manufacturing method according to (10) or (11) above, the binder resin precursor preferably includes a prepolymer having a functional group reactive with an active hydrogen group.

Due to the low Tg of the prepolymer, the use of the prepolymer is expected to improve the fixability at low temperature and to improve the resistance to heat change, the storability and the durability due to extension with an extension agent.

(13) The method for producing a toner according to an embodiment of the present invention, wherein an external additive is added to the resin particles obtained by the method for producing resin particles according to any of the above (10) to (12) .

(14) An image forming apparatus according to an embodiment of the present invention comprises:

electrostatic latent image carrier;

1. Electrostatic latent image forming device used to form an electrostatic latent image on an electrostatic latent image carrier;

A developing device comprising the toner described in (7) above or the developer described in (8) above and using the toner or developer to develop an electrostatic latent image to form a visible image.

a transfer device for transferring the visible image to a recording medium, and

A fixing device for fixing the transmitted visible image on the recording medium.

(15) An imaging method according to an embodiment of the present invention includes:

formation of an electrostatic latent image on an electrostatic latent image carrier;

developing the electrostatic latent image to form a visible image using the toner of (7) above or the developer of (8) above;

transfer the visible image to a recording medium, and

The transmitted visible image is fixed on a recording medium.

Next, it will be described with reference to resin particles, toner, developer, developer storage container, resin particle manufacturing method, toner manufacturing method, image forming apparatus and image forming method according to embodiments of the present invention. drawing. It should be noted that the present invention is not limited to the following embodiments, and within the scope of those skilled in the art, changes such as other embodiments, additions, changes, and deletions may be made as long as the effects of the present invention can be come into play in any aspect, all are included within the scope of the present invention.

As described above, the resin particles according to the embodiment of the present invention can be obtained by a manufacturing method including the following steps a to d.

Step a: dissolving or dispersing at least one of the binder resin and the binder resin precursor, optionally together with a colorant, in an organic solvent to prepare a solution;

Step b: Adding water to the solution to change the phase of the solution from a water-in-oil dispersion to an oil-in-water dispersion;

Step c: removal of the organic solvent from the oil-in-water dispersion to obtain a dispersion of microparticles. and

Step d: Aggregation of the fine particles in the fine particle dispersion to obtain aggregated particles.

The above process and the materials used in the process will be explained below.

[Process a] (oil phase preparation process)

In step a, at least one of the binder resin and the binder resin precursor (hereinafter referred to as "binder resin precursor") is dissolved or dispersed in an organic solvent together with a dye as necessary. Prepare the solution.

In the production method according to the embodiment of the present invention, an oil phase is first produced by dissolving or dispersing, e.g. an oily phase. Resins, dyes and prepolymers in organic solvents. Prepare the oil phase, such as resins and dyes, should be gradually added to the organic solvent with stirring to dissolve or disperse. As the dissolving or dispersing device, a known device may be used, for example, a dispersing device such as a bead mill or a disc mill may be used.

The materials used to make the oil phase will be explained below.

The resin particles according to the embodiment of the present invention are suitable for use as a toner. The toner is obtained by adding external additives to the toner base particles, including resin particles.

Next, the resin particle of the present invention will be described taking as an example a toner as an embodiment of the resin particle of the present invention.

(environmentally friendly resin)

In this specification, biomass-derived resins and recycled resins are sometimes referred to as green resins.

—Resins derived from biomass—

Biomass-derived resins include plant-derived compounds as raw materials. Environmental adaptability and toner quality can be adjusted by adjusting the ratio of crude oil-derived components to plant-derived components in alcoholic and acidic components.

Carbon dust is the concentration of radioactive carbon isotopes¹⁴C (hereinafter "¹⁴concentration of C" in some cases) should be 10.8 pMc or higher, preferably 20 pMc or higher.¹⁴The C concentration is less than 10.8 pMc, generally the biomass is too low.

This here¹⁴The C concentration is represented by the biomass in the following formula.

Biomass (%)=¹⁴C concentration (pMC) x 0.935

This here¹⁴A C concentration of 10.8 pMc or more means that the biomass is 10% or more, and it is also a preferred concentration from the viewpoint of carbon neutrality.

To achieve a biomass level of 10% or higher, biomass-derived materials should be considered for binder resins and waxes in toners.

a measurement method¹⁴The C concentration is not particularly limited and can be appropriately selected to suit a specific application. Special preference is given to radiocarbon dating. The measurement steps in this method are as follows.

First, the toner is burned to reduce carbon dioxide (CO₂) in the toner to obtain graphite (C). After,¹⁴The concentration of C in the graphite was measured by accelerator mass spectrometry (AMS). This AMS measure is e.g. published in Japanese Patent No. 4050051.

This here¹⁴C is found in nature (in the atmosphere) and is absorbed by plants through photosynthesis during plant activity, and¹⁴C concentration in plants vs.¹⁴Atmospheric C concentration (107.5 pMC). But since the end of the plant's life activities,¹⁴photosynthetic uptake of C ceases, and¹⁴concentration of C according to¹⁴C has a half-life of 5730 years.

Since fossil resources originate from living organisms, tens of thousands to hundreds of millions of years have passed since the end of life activities,¹⁴The C concentration was barely detectable.

—Regenerated resin—

Examples of recycled resins include, but are not limited to, polypropylene (PP), polyethylene (PE), polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT).

Among them, PET and PBT are particularly preferred as toner materials.

PET and PBT are recycled products processed into flakes with a weight average molecular weight (Mw) of approx. 30,000 to 100,000. However, PET and PBT are not limited by their molecular weight distribution, composition, method of production, or manner of use.

In addition, PET and PBT are not limited to recycled products, and waste unqualified fibers or PET and PBT granules can also be used. The proportion of recycled PET introduced during the synthesis of the polyester resin can be adjusted to adjust the degree of environmental compatibility and the quality of the toner.

The amorphous polyester resin B used in the present invention preferably contains plant-derived acid and alcohol components to adjust environmental compatibility. Furthermore, polyester resins synthesized from PET and PBT are preferably used.

Propylene glycol is preferably used as the plant-derived alcohol component, and preferably terephthalic acid or succinic acid is used as the plant-derived acid component. These ingredients are not limited as long as the ingredients are derived from plants.

The content of the recycled resin in the binder resin is preferably 55 to 95% by weight, more preferably 60 to 90% by weight. If the content of the recycled resin is less than 55% by weight, fixability, storage, and high-temperature durability may not be achieved. If petroleum-based resins are used to make them, the environmental compatibility rate cannot be improved. If the content exceeds 95% by weight, low-temperature fixing may not be achieved.

The content of the biomass-derived resin in the binder resin is preferably 5% by weight to 45% by weight, more preferably 10% by weight to 40% by weight. If the content of the biomass-derived resin is less than 5% by weight, the petroleum-based resin should be used to achieve low-temperature fixability, but cannot improve the degree of environmental compatibility. If the content of the biomass-derived resin is greater than 45% by weight, fixability, storage, and high-temperature durability may not be achieved. If petroleum-based resins are used to make them, the environmental compatibility rate cannot be improved.

As to the content ratio of recycled resin and biomass-derived resin in the binder resin, recycled resin:biomass-derived resin is preferably 95:5 to 55:45, more preferably 90:10 to 60:40.

If the content of the recycled resin is less than 55% by weight, fixability, storage, and high-temperature durability may not be achieved. If it is implemented with petroleum-based resins, the environmental compatibility rate cannot be improved. If the recycled resin content exceeds 95% by weight, low temperature fixability may not be achieved.

If the content of the biomass-derived resin is less than 5% by weight, the petroleum-based resin should be used to achieve low-temperature fixability, but cannot improve the degree of environmental compatibility. If the content of the biomass-derived resin is greater than 45% by weight, fixability, storage, and high-temperature durability may not be achieved. If petroleum-based resins are used to make them, the environmental compatibility rate cannot be improved.

(resin de polyester)

When the resin is used as a toner to develop an electrostatic latent image in electrophotography, a resin with a polyester skeleton is used to achieve good fixability. Examples of the resin with a polyester backbone include, but are not limited to, polyester resins and block polymers of polyester resins and resins with another backbone. However, polyester resins are more preferably used because the uniformity of the resulting colored resin particles is high.

Examples of polyester resins include, but are not limited to, polymers of ring-opening lactones, polycondensates of hydroxycarboxylic acids, and polycondensates of polyhydric alcohols and polycarboxylic acids. From the point of view of design freedom, polycondensates of polyhydric alcohols and polycarboxylic acids are preferable.

The weight average molecular weight of the polyester resin is usually 1,000 to 30,000, preferably 3,000 to 15,000, more preferably 5,000 to 12,000. If the weight average molecular weight is less than 1,000, the heat-resistant storage stability deteriorates, and if the weight average molecular weight exceeds 30,000, the low-temperature fixability of the toner to produce an electrostatic latent image decreases.

The glass transition temperature of the polyester resin is in the range of 35 °C or more and 80 °C or less, preferably 40 °C or more and 70 °C or less, more preferably 45 °C or more and 65 °C C or less. less. When the glass transition temperature is lower than 35 °C, the resulting colored resin particles may be deformed when placed in a high-temperature environment, such as a high-temperature environment. In the height of summer, the colored resin particles can stick together, inhibiting the original behavior of the particles. When the glass transition temperature is higher than 80°C, the fixability of the colored resin particles deteriorates when it is used as a toner for developing an electrostatic latent image.

Polyol (1) includes diol (1-1) and trivalent or higher polyol (1-2). Polyol (1) preferably contains diol (1-1) alone or a mixture of polyol (1-1) and a small amount of trivalent or higher polyol (1-2).

Examples of diol (1-1) include, but are not limited to, the following:

Alquilenglicol (f.eks. etilenglicol, 1,2-propandiol, 1,3-propandiol, 1,4-butandiol, 1,6-hexandiol);

Alkylene glycol (eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol); cycloalifatiske glycol (for eksempel 1,4-cyclohexandimethanol, hydrogen bisphenol A);

bisphenol (f.eks. bisphenol A, bisphenol F, bisphenol S); alkylene oxide (e.g. ethylene oxide, propylene oxide, butylene oxide) cycloaliphatic dioler form additive; 4,4'-dihydroxybiphenyler som f.eks. 4,4'-dihydroxybiphenyl; bis(hydroxyphenyl)alkanor såsom bis(3-fluoro-4-hydroxyphenyl)methane, 1-phenyl-1,1-bis(3-fluoro-4-hydroxyphenyl)ethane, 2,2-bis(3-fluoro-4- hydroxyphenyl)propane, 2,2-bis(3,5-difluoro-4-hydroxyphenyl)propane (alias: tetrafluorobisphenol A), 2,2-bis(3-hydroxyphenyl)-1,1,1,3,3,3 -hexafluoropropane; bis(4-hydroxyphenyl)ether såsom bis(3-fluoro-4-hydroxyphenyl)ether; og

Alkylene oxide adducts (eg ethylene oxide, propylene oxide, butylene oxide) of the aforementioned bisphenols.

Among these diols, alkylene glycols with 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferred, and alkylene oxide adducts of bisphenols and alkylene oxides with 2 to 12 carbon atoms are particularly preferred. Combinations of alkylene glycols.

Examples of trihydric or higher (1-2) polyhydric alcohols include, among others, polyhydric fatty alcohols having a valence of 3 to 8 (eg, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol); trivalent or higher phenols (eg, triphenol PA, phenol novolac, cresol novolac) and alkylene oxide adducts of the above trivalent or higher polyphenols.

Polycarboxylic acid (2) includes dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). The polycarboxylic acid (2) is preferably dicarboxylic acid (2-1) alone or a mixture of dicarboxylic acid (2-1) and a small amount of trivalent or higher polycarboxylic acid (2-2).

Examples of dicarboxylic acids (2-1) include, but are not limited to, alkylenedicarboxylic acids (eg, succinic acid, adipic acid, sebacic acid); alkenylenedicarboxylic acids (eg, maleic acid, fumaric acid); aromatic dicarboxylic acid; acids (for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid) and 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroisophthalic acid, terephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2-fluoroisophthalic acid, 6-tetrafluoroisophthalic acid, 3,5,6-tetrafluoroterephthalic acid, 5-trifluoromethylisophthalic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, 2,2'-bis( trifluoromethyl)- 4,4'-Biphenyldicarboxylic acid, 3,3-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid, 2,2'-bis(trifluoromethyl)-3,3'-biphenyldicarboxylic acid and hexafluoroisopropylidendiphthalic anhydride. Among these dicarboxylic acids, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

Examples of the trivalent or higher polycarboxylic acid (2-2) include, but are not limited to, aromatic polycarboxylic acids of 9 to 20 carbon atoms (eg, trimellitic acid, pyromellitic acid). Examples of the polycarboxylic acid (2) further include acid anhydrides or lower alkyl esters (eg, methyl ester, ethyl ester, isopropyl ester) of the above compounds which react with polyol (1).

As [OH]/[COOH] equivalent ratio between hydroxyl group [OH] and carboxyl group [COOH], the ratio of polyhydric alcohol to polycarboxylic acid is usually 2/1 to 1/2, preferably 1, 5/1 to 1/1.5. more preferably 1.3/1 to 1/1.3.

(To dye)

As the dye according to the embodiment of the present invention, known dyes and pigments can be used. Examples of dyes include, but are not limited to, carbon black, nigrosine dye, iron black, naphthol yellow, S. Hansa yellow (10G, 5G, G), cadmium yellow, iron oxide yellow , loess, chrome yellow, titanium nitrogen yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), VULCAN FAST YELLOW ( 5G, R), Lemon Yellow Lake, Quinoline Yellow Lake, Anthraquinone Yellow BGL, Isoindolinone Yellow, Iron Oxide Red, Lead Red, Orange Lead, Cadmium Red, Cadmium Mercury Red, Antimony Orange, Red permanent 4R, Red for, Fire Red, Chlorine for PERMANENT RED (F2R, F4R, FRL, FRLL, F4RH), fast scarlet VD, VULCAN FAST RUBINE B, brilliant scarlet G, LITHOL RL BINE GX, permanent red F5R, brilliant carmine 6B , pigmented scarlet 3B, burgundy 5B, toluidine brown, PERMANENT BURGUNDY 1BORD, HAUX 1BORD, HAUX 1BORD, HAUX 1B BON MAROON LIGHT, BON MAROON MEDIUM, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red. Chrome Vermilion, Benzidine Orange, Polynaphthyl Orange, Oil Orange, Cobalt Blue, Sky Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue , phthalocyanine blue, rapid sky blue, Indance Lin blue (RS, BC), indigo, ultramarine blue, Prussian blue, anthraquinone blue, rapid violet B, methyl purple lake, cobalt violet, manganese violet, dioxane violet , Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Cordierite, Emerald Green, Naphthol Green Pigment Green B. Gold Green, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Oxide , Lithopone and their mixtures.

(organic solvents)

The organic solvent is preferably a volatile solvent with a boiling point below 100°C, since it facilitates subsequent removal of the organic solvent. Examples of such organic solvents include, but are not limited to, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylene, methyl acetate. , ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone, methanol, ethanol and isopropanol. Each of these solvents can be used alone or in combination with other solvents. When the resin dissolved or dispersed in the organic solvent has a polyester skeleton, the organic solvent is preferably selected from ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, or ketone solvents such as methyl ester and ethyl. Ketone and methyl isobutyl ketone, high solubility. In particular, methyl acetate, ethyl acetate and methyl ethyl ketone are preferred due to their high elimination properties.

(prepolymer)

The prepolymer (reactive precursor) can be, for example, a polyester with a group reactive with an active hydrogen group. Examples of groups reactive with active hydrogen groups include, among others, isocyanate groups, epoxy groups, carboxyl groups, and acid chloride groups. Among these groups, an isocyanate group is preferable because a urethane bond or a urea bond can be introduced into the amorphous polyester resin.

The prepolymer may have a branched structure imparted by at least one trivalent or higher alcohol and one trivalent or higher carboxylic acid.

Examples of polyester resins with isocyanate groups include, among others, reaction products of polyester resins with active hydrogen groups and polyisocyanates. The polyester resin with active hydrogen groups can be obtained e.g. polycondensation of diols, dicarboxylic acids and at least one of trivalent or higher alcohols and trivalent or higher carboxylic acids. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched chain structure to the polyester resin with an isocyanate group.

Examples of diols include, but are not limited to: aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3- methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-decadialkylene glycol; glycols with an oxyalkylene group, such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Alicyclic diols formed by addition of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; ethylene oxide, alkylene oxide adducts of bisphenols formed by adduction of alkylene oxides such as alkylene oxides and butylene oxide. Among them, aliphatic diols having 3 to 10 carbon atoms, such as 1,2-propanediol and 1,3-propanediol, are preferred to make the glass transition temperature of polyester resin 20°C. or lower. Ethylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, and 3-methyl-1,5-pentanediol. More preferably, the diol represents 50 mol% or more of the alcohol component of the resin. Each of these diols can be used alone or in combination with other diols.

Ideally, the polyester resin is an amorphous resin. In addition, a steric hindrance can be applied to the resin chain so that the viscosity of the melt at the time of fixing the toner is lowered and the toner more easily exhibits a low-temperature fixability. Therefore, the main chain of the aliphatic diol preferably has a structure represented by the following general formula (1).

[where R₁y R₂Each independently represents a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, n represents an odd number from 3 to 9, and each R₁y R₂same or different from each other in n repeat units]

Here, the main chain of the aliphatic diol according to the embodiment of the present invention refers to a carbon chain connecting the two hydroxyl groups with the smallest number of carbon atoms in the aliphatic diol. When the number of carbon atoms in the main chain is an odd number, the crystallinity decreases due to evenness, which is preferable. When at least one of the alkyl groups of 1 to 3 carbon atoms is contained in the side chain, the interaction energy between the main chain molecules is lowered due to steric hindrance, which is more preferable.

Examples of dicarboxylic acids include, but are not limited to: aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid; aromatic dicarboxylic acids such as formic acid, terephthalic acid and naphthalic acid. In addition, acid anhydrides, lower (C1-C3) alkyl esters and their halides can also be used. More importantly, to adjust the Tg of the polyester resin at 20°C or below, there are 4 or more and 12 or more aliphatic dicarboxylic acids. Fewer carbon atoms are preferred. More preferably, the dicarboxylic acid represents 50% by weight or more of the carboxylic acid component of the resin. Each of these dicarboxylic acids can be used alone or in combination with others.

Examples of alcohols with more than three valences include, but are not limited to: fatty alcohols with more than three valences, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol, polyphenols with more than three valences, such as triphenol PA, phenol novolac, and cresol novolac , and alkylene oxide adducts of trivalent or higher polyphenols, for example, alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide added to trivalent or higher valent polyphenols.

Examples of trivalent or higher carboxylic acids include, but are not limited to, trivalent or higher aromatic carboxylic acids. Particularly preferred are trivalent or higher aromatic carboxylic acids of 9 to 20 carbon atoms, such as trimellitic acid and pyromellitic acid. In addition, acid anhydrides, lower (C1-C3) alkyl esters and their halides can also be used.

Examples of polyisocyanates include, but are not limited to, diisocyanates and trivalent or higher isocyanates.

The polyisocyanate is not particularly limited and can be appropriately selected to suit a specific application. Examples of polyisocyanates include, but are not limited to:

Aromatic diisocyanates such as 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI), crude TDI, 2,4'- and/or 4,4'-diisocyanate of diphenylmethane (MDI), crude MDT [compound of crude diaminophenylmethane phosgene [condensate of formaldehyde with aromatic amine (aniline) or mixtures thereof: diaminophenylmethane with a small amount (for example, 5 to 20% by weight) of a polyamine trifunctional or higher functional]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate and m- and p-isocyanatophenylsulfonyl isocyanate;

Ethylenediisocyanato, tetramethylenediisocyanato, hexamethylenediisocyanato (HDI), dodecamethylenediisocyanato, 1,6,11-undecantriisocyanato, 2,2,4-triisocyanato Methylhexamethylenediisocyanato, lysine-diisocyanato, 6-methyl-diisocyanato, 2,2,4-triisocyanato isocyanatoethyl) fumarate, bis (2-isocyanatocyanatoethyl)carbonate of 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanate) Cycloaliphatic diisocyanates such as cyanatodicarboxylene-4-cyclohexylene and 2,5- and 2-diisocyanates ,6-norbornene;

araliphatic diisocyanates, such as m-y p-xylylenediisocyanate (XDI) y α,α,α',α'-tetramethylxylylenediisocyanate (TMXDI);

lysine triisocyanate, modified trivalent or higher alcohol diisocyanate and other trivalent or higher polyisocyanates; and

Modified products of these isocyanates and mixtures of two or more of these polyisocyanates. Examples of modified isocyanates include, but are not limited to, those having urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretdione groups, uretonimine groups, isocyanate groups, modified urate- or oxazolidinone-based isocyanates.

(tax control agent)

For example, charge control agents can be added to the oil phase.

As the charge control agent, all known charge control agents can be used. Examples of charge regulating agents include, but are not limited to, nigrosin dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including quaternary modified with fluorine), phosphorus and phosphorus-containing compounds, tungsten and tungsten-containing compounds, fluorine activators, metal salts of salicylic acid and metal salts of salicylic acid derivatives. Specific examples of charge regulating agents include, but are not limited to, BONTRON 03 nigrosine dye, BONTRON P-51 quaternary ammonium salt, BONTRON S-34 metal-containing azo dye, BONTRON E-82 naphthoic acid metal complex, BONTRON E-82 metal complex BONTRON E1-84 salicylic acid, BONTRON E-89 phenolic condensate (manufactured by Oriental Chemical Industry Co., Ltd.); TP-302 and TP-415 quaternary ammonium molybdenum complexes (manufactured by Hodogay a Chemical Co., Ltd.); COPY CH4ARGE PSY quaternary ammonium salt VP2038, derivative of triphenylmethane COPY BLUE PR, COPY CHARGE NEG quaternary ammonium salt VP2036 and COPY CHARGE NX VP434 (manufactured by Hoechst AG): LRA-901 and LR-147 boron complex manufactured by Japan Calchufacture AG. , Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments, and polymeric compounds with functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium groups.

The amount of charge control agent is determined so that the charge control agent can perform its function without inhibiting binding ability. The charge control agent preferably constitutes 0.5% to 5% by weight of the toner, preferably 0.8% to 3% by weight.

[Process b] (phase inversion and emulsification process)

In step b, water is added to the solution obtained in step a to change the phase of the solution from a water-in-oil dispersion to an oil-in-water dispersion.

In the present description, the oily phase is neutralized, for example, with sulfuric acid. Ammonia water is added with deionized water to emulsify the solution phase so that the solution phase changes from a water-in-oil dispersion to a water-in-oil dispersion and a fine particle dispersion is obtained.

[Process c] (Solvent removal process)

In step c, the organic solvent is removed from the oil-in-water dispersion obtained in step b to obtain a fine particle dispersion.

To remove the organic solvent from the fine particle dispersion, a method of gradually raising the temperature of the entire system while stirring to completely evaporate and remove the organic solvent from the liquid droplets can be used.

Alternatively, the obtained fine particle dispersion can be injected in a dry atmosphere with stirring and the organic solvent can be completely removed from the droplets. Alternatively, the fine particle dispersion can be distilled with stirring to evaporate and remove the organic solvent. The last two objectives can also be used in combination with the first.

Examples of the dry atmosphere in which the fine particle dispersion is sprayed include, but are not limited to, heated gaseous substances such as air, nitrogen, carbon dioxide gas, and flue gas. In particular, a gaseous substance heated above the boiling point of the solvent with the highest boiling point among the solvents used is often used. The desired quality can be achieved with short processing times using spray driers, belt driers or rotary kilns.

The aforementioned method allows to obtain a dispersion of fine particles.

[process d] (merger process)

In step d, fine particles in the fine particle dispersion obtained in step c are aggregated to obtain aggregate particles.

The microparticles are aggregated while stirring the microparticle dispersion until the diameter of the aggregate reaches a prescribed particle diameter. For aggregation, existing methods such as addition of a coagulant and pH adjustment can be used. When adding the coagulant, the coagulant can be added directly, but it is more preferable to add the aqueous solution of the coagulant after preparation, because local high concentration can be avoided. Furthermore, it is preferable to gradually add the added salt while observing the particle diameter of the added particles.

The temperature of the dispersion liquid at the time of aggregation is preferably around the Tg of the resin used. When the liquid temperature is too low, the coagulation does not go far enough and the efficiency deteriorates. When the liquid temperature is too high, the coagulation speed becomes fast and the particle size distribution is poor, such as the generation of coarse particles.

The aggregation ends when the particle size reaches the desired size. Examples of methods for terminating aggregation include, but are not limited to, addition of salts or low ionic chelating agents, adjustment of pH, lowering of reactor temperature. Dispersion, add a large amount of aqueous medium to dilute.

The above method makes it possible to obtain the dispersion of aggregate particles.

During aggregation, wax can be added as a release agent or crystalline resins can be added for low temperature fixation. In this case, a dispersion of wax dispersed in an aqueous medium or a dispersion of crystalline resin dispersed in the same manner is prepared, mixed with the above dispersion of fine particles, and aggregated to obtain uniformly aggregated particles. Dispersed wax or crystalline resin.

The coagulant, the wax and the crystalline resin will be explained below.

(coagulant)

Known coagulants can be used as coagulants. Examples of coagulants include, but are not limited to, metal salts of monovalent metals such as sodium and potassium, metal salts of divalent metals such as calcium and magnesium, and metal salts of trivalent metals such as iron and aluminum.

By adding metal salts as coagulants, metal ions act as metal crosslinkers and polymer chains aggregate through metal ion crosslinks. Metal crosslinking of metal crosslinking agents is expected to improve resistance to thermal change, storage strength and durability.

(cera)

The wax is not particularly limited and can be appropriately selected to suit a specific application, but a release agent with a low melting point of 50°C to 120°C is preferred. A release agent with a low melting point, when dispersed in a resin, acts effectively at the interface between the fuser roller and the toner, thereby improving resistance to thermal compensation.

Preferred examples of release agents include, but are not limited to, solder and wax. Examples of solders and waxes include, but are not limited to: natural waxes such as vegetable waxes such as carnauba wax, cotton wax, sumac wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and ozokerite, and petroleum waxes such as paraffin wax, microcrystalline wax, and vaseline wax. In addition to these natural waxes, examples of waxes include, but are not limited to: synthetic hydrocarbon waxes such as Fischer-Tropsch waxes and polyethylene waxes, synthetic waxes such as ester waxes, ketone waxes, ether waxes, and Similar. In addition, the following substances can also be used: fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imine, chlorinated hydrocarbons, homopolymers or copolymers of polyacrylates, such as poly n-stearyl methacrylate and poly -n-lauryl methacrylate, which are low molecular weight crystalline polymeric resins (eg, n-stearyl acrylate-ethyl methacrylate copolymers); Alkyl crystalline polymers. Each of these types of wax can be used alone or in combination with the others.

The melting point of the wax is not particularly limited and can be appropriately selected according to the use, but it is preferably 50°C to 120°C, more preferably 60°C to 90°C. C. or lower. If the melting point is 50 °C or higher, it can prevent the wax from adversely affecting the heat-resistant storage stability, and if the melting point is 120 °C or lower, it can avoid the problem of cold change during the low melting point. It can effectively prevent excessive temperature.

The melt viscosity of the wax is measured at a temperature 20°C higher than the melting point of the wax, and is preferably 5 cps to 1000 cps, more preferably 10 cps to 100 cps. If the melt viscosity is 5 cps or more, the grinding property of the shape can be prevented from deteriorating, and if the melt viscosity is 1000 cps or less, the effects of heat change resistance and low temperature fixing ability can be fully displayed.

The content of the wax in the toner is not particularly limited and can be appropriately selected to suit a specific application, but it is preferably 0% by weight or more and 40% by weight or less, more preferably 3% by weight or more and 30% by weight or more. % in weigh. by weight or less. If the content is 40% by mass or less, deterioration of fluidity of toner can be prevented.

(Crystalline polyester resin)

Crystalline polyester resins are obtained from polyhydric alcohols and polycarboxylic acids, such as polycarboxylic acids, polycarboxylic anhydrides, and polycarboxylic esters or derivatives thereof. In the present invention, the crystalline polyester resin refers to a resin obtained from a polyhydric alcohol and a polycarboxylic acid, such as polycarboxylic acid, polycarboxylic anhydride and polycarboxylic acid ester or derivatives thereof as described above. Modified polyester resins, such as prepolymers and resins obtained by at least one of crosslinking and elongation of prepolymers, do not belong to crystalline polyester resins.

<

The polyol is not particularly limited and can be appropriately selected to suit a particular application. Examples of polyols include, but are not limited to, diols and trivalent or higher alcohols. Examples of diols include, but are not limited to, saturated aliphatic diols. Examples of saturated aliphatic diols include, but are not limited to, straight chain saturated aliphatic diols and branched saturated aliphatic diols. Among them, straight chain saturated aliphatic diols are preferable, and straight chain saturated aliphatic diols having 2 to 12 carbon atoms are more preferable. Branched saturated aliphatic diols can reduce crystallinity and further lower the melting point of crystalline polyester resins. Practical materials for saturated aliphatic diols with more than 12 carbon atoms are not readily available.

Examples of saturated aliphatic diols include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 14-diol and 14-octadecanediol. Among these diols, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are resins. with high crystallinity and excellent fast melting. properties

Examples of trivalent or higher alcohols include, but are not limited to, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. Each of these polyols can be used alone or in combination with other polyols.

<>

The polycarboxylic acid is not particularly limited and can be appropriately selected to suit a particular application. Examples of polyvalent carboxylic acids include, but are not limited to, dicarboxylic acids and trivalent or higher carboxylic acids. Examples of dicarboxylic acids include, but are not limited to, saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, aromatic dicarboxylic acids such as terephthalic acid, 2,6- and malic acid, mesaconic acid. Furthermore, examples include, but are not limited to, lower (C1-C3)alkyl esters and anhydrides of these dicarboxylic acids.

Examples of trivalent or higher carboxylic acids include, but are not limited to, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and lower (C1-C3) anhydrides and esters of I rent them. Each of these carboxylic acids can be used alone or in combination with other carboxylic acids.

The crystalline polyester resin preferably includes a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. Such a crystalline polyester resin has a high degree of crystallinity and excellent fast melting properties, and therefore exhibits excellent low-temperature fixing properties. As a method of controlling the crystallinity and softening point of a crystalline polyester resin, e.g. a non-polyester resin made by polycondensation between an alcohol component, including a polyhydric alcohol with a valency of 3 or more, such as glycerin, and an acid component, including a linear Polyester polycarboxylic acid. When synthesizing polyester, it is designed to use acids with a valence greater than 3, such as trimellitic anhydride.

The molecular structure of the crystalline polyester resin according to the embodiment of the present invention can be confirmed by solid or solution NMR measurement and X-ray diffraction, gas chromatography/mass spectrometry (GC/MS), liquid chromatography /mass spectrometry (LC/MS) or infrared spectroscopy (IR). Briefly, however, the molecular structure can be confirmed, for example, by the absorption at 965±10 cm due to the δCH (out-of-plane bending vibration) of the alkene.⁻¹o 990±10cm⁻¹in the infrared absorption spectrum.

As the molecular weight distribution becomes narrower and the molecular weight becomes lower, the fixability at low temperature improves. As the amount of the low molecular weight component increases, the heat-resistant storage stability deteriorates. Therefore, as a result of intensive research, it is preferable to use the gel permeation chromatography (GPC) molecular weight distribution diagram with log(M) on the horizontal axis and %wt on the vertical axis relative to with the concentration of o-crystalline dichloride. polyester resin. The benzene soluble component has a peak in the range of 3.5 to 4.0, half peak width is 1.5 or less, weight average molecular weight (Mw) is 3000 to 30,000, the number average molecular weight (Mn) is 1000 to 10,000, Mw/Mn ratio is 1-10.

More preferably, the weight average molecular weight (%Mw) is 5000 to 15000, the number average molecular weight (Mn) is 2000 to 10000 and the Mw/Mn ratio is 1 to 5.

From the point of view of the affinity between paper and resin, the acid number of crystalline polyester resin is preferably 5 mgKOH/g or more to achieve the desired level of low-temperature fixability, and the acid number of Acidity of crystalline polyester resin is preferably 7 mgKOH/g.g above to pass phase inversion and emulsification. On the other hand, the acid number of the crystalline polyester resin is preferably 45 mgKOH/g or less to improve the resistance to heat exchange. In order to achieve a predetermined low-temperature fixability and load-bearing capacity, the hydroxyl number of the crystalline polymer is preferably 0 mgKOH/g or more and 50 mgKOH/g or less, more preferably 5 mgKOH/g or more. and 50 mgKOH/g or less. further. less.

(fusion process)

Then, the obtained aggregate particles are fused by heat treatment to reduce irregularities. For melting, the dispersion of aggregated particles must be heated while stirring. The liquid temperature is preferably around a temperature higher than the Tg of the resin.

(washing and drying process)

Since the toner particle dispersion liquid obtained by the above method contains by-products such as coagulated salts in addition to the toner particles, washing is performed to individually remove the toner particles from the dispersion liquid. The method for washing toner particles is not particularly limited, and examples of the method include, but are not limited to, centrifugal separation, reduced pressure filtration, and filter press. In both methods a cake of toner particles is obtained. If the washing is insufficient in a single operation, the process of redispersing the obtained filter cake in an aqueous medium to produce a suspension and extracting the toner particles can be repeated by one of the above methods. In the case of vacuum filtration or filter press washing, an aqueous medium may be passed through the filter cake to wash by-products from the resin particles.

As the aqueous medium used in the washing step, water or a mixed solvent of water and alcohols such as methanol and ethanol is used. Water is preferable considering the cost and environmental impact caused by wastewater treatment.

After the washing process, the toner particles contain a large amount of aqueous medium. The toner particles can be isolated by removing the aqueous medium by drying. Drying can be accomplished using a dryer such as a spray dryer, vacuum freeze dryer, reduced pressure dryer, stationary rack dryer, moving rack dryer, fluid bed dryer, rotary dryer, or rotary dryer. shake dryer. The dried toner particles are preferably dried until the residual moisture content is less than 1%. In the event that dry resin particles are objectionable in the form of soft aggregate, the soft aggregate can be broken up and loosened using equipment such as a jet mill, Henschel blender, super blender, coffee grinder, OSTER BLENDER, and food processor.

(annealing process)

When adding crystalline resin, annealing treatment should be carried out after drying to separate non-crystalline resin and crystalline resin phases to improve fixability. Specifically, it should be kept at a temperature close to the Tg of the crystalline resin for at least 10 hours.

(External additive application process)

E.g. Inorganic fine particles, polymer fine particles and cleaning aids can be added and mixed into the toner particles obtained in the present invention in order to provide fluidity, loadability and cleaning properties.

Specific examples of the mixing method include, but are not limited to, a method of applying an impact force to the mixture using a high-speed rotating blade and a method of accelerating the mixing by accelerating the mixture in an air stream of high speed. . Particles or composite particles collide with each other or with collision plates. Examples of useful devices include, but are not limited to, ANGMILL (manufactured by Hosokawa Micron Corporation), I-TYPE MILL modified to reduce spray air pressure (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), HYBRIDIZATION SYSTEM ( manufactured by ) of Nara Machinery Co., Ltd.), KRYPTRON SYSTEM (manufactured by Kawasaki Heavy Industries, Ltd.), and automatic mortars.

(external additive)

Preferably, the primary particle diameter of the inorganic fine particles is not less than 5 nm and not more than 2 µm, more preferably not less than 5 nm and not more than 500 nm. Preferably, the specific surface area measured by the BET method is 20 m²/g or more and 500 m²/g or less. Preferably, the use ratio of the inorganic fine particles is 0.01 to 5% by weight based on the toner. Specific examples of inorganic particles include, but are not limited to, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica , calcareous sand, diatomaceous earth. , chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.

Examples of fine polymer particles include, but are not limited to, polystyrene particles obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; methacrylate or acrylate copolymer particles; polysiloxane, benzoguanamine, polycondensate particles such as nylon; and thermosetting resin polymer particles.

The fluidizing agent can be surface-treated to increase its hydrophobicity to prevent deterioration of fluidity and load-bearing capacity even under high humidity conditions. Preferred examples of surface treatment agents include, but are not limited to, silane coupling agents, silylating agents, silane coupling agents with fluorinated alkyl groups, organic titanate coupling agents, aluminum coupling agents, silicone oils and modified silicone oils.

When developer remaining on the photoreceptor or primary transfer medium after image transfer is removed, examples of builders include, but are not limited to: metal salts of fatty acids such as zinc stearate and stearate calcium; and polymer fines produced by soap-free emulsion polymerization, such as polymethylmethacrylate fines and polystyrene fines. Such fine polymer particles preferably have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 µm.

(Developer)

The developer according to the embodiment of the present invention contains the toner according to the embodiment of the present invention. The developer may be a one-component developer or a two-component developer in which a toner is mixed with a carrier. When the developer is used for a high-speed printer compatible with the latest increase in information processing speed, a two-component developer is particularly preferable from the standpoint of prolonging the life of the printer.

In the case of a one-component developer using the above-mentioned toner, the variation in the diameter of the toner particles is small even if toner consumption and recharging are repeated, and no toner formation occurs in the developer roller. film, the toner is not contaminated. Integration with layer thickness regulating elements such as blades for thinning the toner layer, good and stable image and developability can be achieved even after long-term use (shaking) of the developing device.

In the case of a two-component developer using the above-mentioned toners, the fluctuations in the diameter of the toner particles in the developer, even after repeated use and recharging of the toner for a long time, are small and achievable Good and Se It can achieve stable development capacity even after long-term shaking of the development team.

The developer according to the embodiment of the present invention can also be used as a supplemental developer.

The carrier is not particularly limited and can be appropriately selected to suit a specific application. Preferably, the support includes a core material and a layer of resin covering the core material.

(developer repository)

The developer storage container for storing the developer according to the embodiment of the present invention is not particularly limited and can be appropriately selected from known containers. For example, a developer stock container may include a container body and a lid.

The container body is e.g. not particularly limited. Size, shape, construction and material. The container body is preferably cylindrical. In particular, on the inner peripheral surface of the container body, spiral-shaped bumps and depressions are formed so that the developer can move toward the outlet port side when the container body rotates. More preferably, some or all of the helical irregularities have an accordion function. Furthermore, the container body is preferably made of a material with good dimensional accuracy. Examples of such materials include, but are not limited to, resin materials such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.

The developer storage container is easy to store, transport, and dispose of. Accordingly, a developer storage container is removably mounted to a process cartridge or imaging apparatus described below for supplying developer thereto.

Next, aspects of an image forming method performed by an image forming apparatus according to an embodiment of the present invention will be described below with reference to Fig. 1.1Although a printer is shown as an example of an image forming apparatus according to an embodiment of the present invention, the image forming apparatus is not particularly limited thereto as long as the image forming apparatus can form an image using toner as a toner. . Ideal for photocopiers, fax machines or multifunction devices.

The imaging apparatus includes a paper feeder210, conveyer belt220imaging device230, transmission unit240, and the accessory250.

document feeder210Includes a paper tray.211The P paper (used as the recording medium) to be fed and the paper feed rollers are stacked on it212Ejecting the paper stacked in the paper feeder P211one by one.

transporter220Contains: one roll221Paper feed P fed by the paper feed roller212against the carrier240A pair of synchronous rollers222Supports the leading edge of the P paper that is conveyed by the roller221Send P sheet to transfer unit240at a predetermined time and output rollers223Output of a P sheet with a solid color toner image to an output tray224.

imaging device230Including: from left to right in the image.1At predetermined intervals, imaging unit Y forms an image using a developer containing a yellow toner, imaging unit C forms an image using a developer containing a cyan toner, and imaging unit M forms an image using a developer containing contains a magenta toner. . a toner and an imaging unit K that forms an image using a developer containing black toner; and an irradiator233emitting light L. Imaging units Y, C, M, and K contain their own magazines232Y,232C,232command, sum232K and their respective development units180Y,180C,180command, sum180K. Radio233and charger232Y,232C,232command, sum232K works together as an electrostatic modeling device.

Hereinafter, any of the imaging units Y, C, M and K will be referred to simply as the imaging unit.

The developer contains toner and carrier. The four imaging units Y, C, M and K have basically the same mechanical configuration except for the developer they contain.

drive unit240Indeholder: a drive roll241;Roll included242intermediate conveyor belt243Turn counterclockwise in the figure.1According to drive roll drive241;Main transfer roller244Y,244C,244command, sum244K faces the respective arrangement of photosensitive drum231Y,2311C,231command, sum231K-belt intermediate transfer belt243in the middle and a secondary opposite roll245and secondary transfer roller246Place in front of the intermediate transfer belt243Enter the place where the toner image is transferred to the paper.

Invent250Includes: Strap251A heater is installed inside to heat the sheet P; and a press roll252rotatably pressed against the fixing strap251to form a space between them. The color toner image on the P paper is heated and pressurized, and the color toner image is fixed. P paper on which a color toner image has been fused is ejected to the output tray224through the exit roller223, and a series of imaging processes are completed.

(treatment box)

A process cartridge according to one embodiment of the present invention is designed to be removably mounted in an imaging apparatus. The process cartridge includes at least one electrostatic latent image-carrying body configured to carry an electrostatic latent image and a developing device configured to develop the electrostatic latent image carried on the electrostatic latent image-carrying body into a toner image with a developer. according to one embodiment of the device of the present invention. this invention The process cartridge according to the embodiment of the present invention may optionally further comprise other devices.

A developer device includes at least one developer container that contains a developer according to one embodiment of the present invention and a developer carrier that carries and transports the developer contained in the developer container. The developing device may further include, for example, an adjustment device for adjusting the thickness of the developing layer carried on the developing support.

As shown in the picture.2Fig. 1 is a diagram illustrating a process cartridge in accordance with one embodiment of the present invention. process chart110including photosensitive drum10Exposure L, crown charger58, develop unity40, transfer roller80and cleaning agentsafter 90.a number95Represents a transfer table.

Embodiments of the present invention will be described in more detail below in connection with examples, but are not limited to these examples. In the following description, "parts" and "%" represent "parts by mass" and "percentage by mass", respectively.

170 parts of isophorodiamine and 75 parts of methyl ethyl ketone were added to a reaction vessel equipped with a stirrer and a thermometer and reacted at 50°C for 5 hours. This is how [ketimine compound] was produced.

[The ketimine compound] was found to have an amine value of 418 mgKOH/g.

Charge 3-methyl-1,5-pentanediol, isophthalic acid, and sebacic acid of vegetable origin together with titanium tetraisopropoxide into a reaction vessel equipped with a cooling tube, stirrer, and nitrogen inlet tube (1000 ppm, depending on the ratio of OH ) /COOL-H from the hydroxyl group of the resin to the carboxyl group of 1, 1), the diol component contains 100 mol% 3-methyl-1,5-pentanediol, and the dicarboxylic acid component contains 66 % mol of isophthalic acid and sebacic acid is 34 mol%, and the amount of trimethylolpropane in all monomers is 1.5 mol%. The contents of the vessel were heated to 200°C for ca. 4 hours, then at 230°C for 2 hours, and the reaction was continued until no more effluent was produced. The contents of the container were further reacted under a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester A].

Next, the obtained [polyester intermediate A] and isophorone diisocyanate (IPDI) were added to a mixing tank equipped with a cooling tube, a stirrer and a nitrogen gas introduction tube in a molar ratio (isocyanate group in IPDI/hydroxyl group in the intermediate ) in the reaction vessel. polyester) 2.0. The contents of the vessel were diluted with ethyl acetate into a 50% ethyl acetate solution and allowed to react at 100°C for 5 hours. Thus [prepolymer A] was prepared.

In a four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, recycled PET flakes, plant-derived propylene glycol, 2 mole petroleum-derived bisphenol A ethylene oxide adduct , plant terephthalic, and petroleum adipic acid give a molar ratio of recycled PET flake (ethylene glycol unit in PET), plant-based propylene glycol, and ethylene oxide bisphenol adduct of 2 moles of 32:21:47, the molar ratio of sheet -such as recycled PET (terephthalic acid unit in PET), plant-derived terephthalic acid and adipic acid is 32:21:47, and the molar ratio of a hydroxyl group and a carboxyl group OH/COOH is 1, 3. The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol % based on the total components of the resin, and it was reacted under normal pressure and 180 °C for 3 hours, thus [ amorphous polyester resin preparation B-1].

In a four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, recycled PET flakes, plant-derived propylene glycol, 2 mole petroleum-derived bisphenol A ethylene oxide adduct , plant-derived terephthalic, and adipic acid from petroleum make the molar ratio of recycled PET flake (ethylene glycol unit in PET), plant-derived propylene glycol, and ethylene oxide adduct of 2 moles of bisphenol to be 51:30:19 , the molar ratio of recycled PET (terephthalic acid unit in PET), plant-derived terephthalic acid and adipic acid is 51:30:19, and the molar ratio of a hydroxyl group and a carboxyl group OH/COOH is 1.3 . The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol% based on the total resin components, and reacted at normal pressure and 180°C for 3 hours. Thus [amorphous polyester resin B-2] was prepared.

The terephthalic acid source and adipic acid petroleum source make the molar ratio of recycled flake PET (ethylene glycol unit in PET), propylene glycol plant source, and 2 mole bisphenol ethylene oxide adduct to be 56:30: 14, the molar ratio of recycled flake PET (terephthalic acid unit in PET) to plant-derived terephthalic acid and adipic acid is 56:30:14, and the molar ratio is the ratio of hydroxyl and carboxyl-OH/ COOH is 1.3. The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol% based on the total resin components, and reacted at normal pressure and 180°C for 3 hours. Thus [amorphous polyester resin B-3] was prepared.

In a four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, recycled PET flakes, plant-derived propylene glycol, 2 moles of petroleum-derived bisphenol A ethylene oxide adduct , plant The molar ratio of recycled PET flake (ethylene glycol unit in PET), plant-derived propylene glycol, and 2-mol bisphenol ethylene oxide adduct of petroleum-derived terephthalic acid and adipic acid was 63:30:7, the molar ratio of recycled material in the form of PET sheet (terephthalic acid unit in PET), plant-derived terephthalic acid and adipic acid is 63:30:7, and the molar ratio between a hydroxyl group and a carboxyl OH/COOH group is 1,3. The mixture was reacted with tetraisopropoxytitanium (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mm-1 g for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol% based on the total resin components, and reacted at normal pressure and 180°C for 3 hours. Thus [amorphous polyester resin B-4] was prepared.

In a four-necked flask equipped with a nitrogen gas inlet tube, dehydration tube, stirrer, and thermocouple, recycled PET flakes, plant-derived propylene glycol, 2 moles of ethylene oxide adduct of bisphenol A derived from petroleum, plant-based Terephthalic acid and adipic acid of petroleum origin allow the molar ratio of recycled PET flake (ethylene glycol unit in PET), propylene glycol of plant origin, and 2-mole bisphenol-ethylene oxide adducts to be of 16:37:47, the molar ratio of recycled flake PET (terephthalic acid unit in PET), plant-derived terephthalic acid and adipic acid is 16:37:47, and the OF/COOH molar ratio of a hydroxyl group to a carboxyl group is 1,3. The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol% based on the total resin components, and reacted at normal pressure and 180°C for 3 hours. Thus [amorphous polyester resin B-5] was prepared.

The terephthalic acid source and petroleum source of adipic acid make the molar ratio of recycled PET flake (ethylene glycol -unit in PET), plant source of propylene glycol, and 2-mol bisphenol-ethylene oxide adduct of 24:29:47 , the molar ratio of recycled PET in sheet form (terephthalic acid unit in PET), plant-derived terephthalic acid and adipic acid is 24:29:47, and the molar ratio of a hydroxyl group and a carboxyl group OH/ COOH is 1.3. The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at normal pressure and 230°C for 8 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 4 hours. Subsequently, trimellitic anhydride was added to the reaction vessel so that the content of trimellitic anhydride was 1 mol% based on the total resin components, and reacted at normal pressure and 180°C for 3 hours. Thus [amorphous polyester resin B-6] was prepared.

The compositions of the amorphous polyester resins B-1 to B-6 are listed in Table 1.

Add plant-derived tallow acid and 1,6-hexanediol to a 5-liter, four-necked flask equipped with a nitrogen gas inlet tube, dehydration tube, stirrer, and thermocouple such that the hydroxyl group molar ratio is the same as that of the carboxyl group 01-1/COOH is 0.9. The mixture was reacted with titanium tetraisopropoxide (500 ppm based on resin component) at 180°C for 10 hours, then heated at 200°C for 3 hours, and then reacted at 8.3 kPa for 10 hours. . 2 hours. Thus [crystalline polyester resin C] was prepared.

In a reaction vessel equipped with a stirrer and thermometer, 683 parts of water, 11 barrels of sodium sulfate salt with ethylene oxide adduct of methacrylic acid (ELEMINOL RS-30, manufactured by Sanyo Chemical Industries, Ltd.) , 138 parts styrene, 138 parts methacrylic acid, 1 part ammonium persulfate. The mixture was stirred at 400 rpm for 15 minutes. A white emulsion was thus produced. Then, the temperature of the reaction system was raised to 75°C, and the reaction was carried out for 5 hours. Then, 30 parts of a 1% aqueous solution of ammonium persulfate were added to the reactor, and aging was carried out at 75°C for 5 hours. Thus, [vinyl resin dispersion liquid] was prepared.

First, 1200 parts water, 500 parts carbon black (PRINTEX 35, manufactured by Degussa AG) [DBP oil absorption = 42 ml/100 mg, pH = 9.5], [amorphous polyester resin B-1 ] 500 parts] used Henschel A. mixer (manufactured by NIPPON COKE & ENGINEERING CO., LTD.) mixed. The resulting mixture was kneaded at 150°C for 30 minutes with double rollers, then cooled with a roller press and pulverized with a pulverizer. This is how the [master batch] was prepared.

42 parts of carnauba wax (RN-5, manufactured by CERARICA NODA Co., Ltd., a vegetable wax with a melting point of 82°C) used as a release agent were filled into a container equipped with a stirrer and a thermometer. Added 420 parts to ethyl acetate, heated to 80°C, held at 80°C for 5 hours with stirring, and cooled to 30°C for 1 hour. The resulting liquid was subjected to a dispersion treatment at a liquid feed rate of 1 kg using a bead mill (manufactured by ULTRAVISCOMILL, ATM EX CO., LTD.) filled with 80 volume % zirconium beads of 0.5mm in diameter. /hour at a peripheral velocity of the disk of 6 m/s. This dispersion process was carried out in 3 steps. Thus [wax dispersion liquid] was prepared.

In a vessel equipped with a stirrer and a thermometer, 308 parts of [Crystalline Polyester Resin C] and 1,900 parts of ethyl acetate were charged. Then, with stirring, the mixture was heated to 80°C and held at 80°C for 5 hours and then cooled to 30°C for 1 hour. Next, dispersion treatment was carried out in 3 steps using a bead mill (manufactured by ULTRAVISCOMILL, AIMEX CO., LTD.) filled with 80% by volume of zirconia beads with a diameter of 0.5 mm. . This is how [Crystalline Polyester Dispersion Liquid] was prepared.

165 parts [wax dispersion liquid], 245 parts [amorphous polyester resin B-1], 270 parts ethyl acetate and 75 parts [masterbatch] were mixed using TK HOMOMIXER (manufactured by PRIMIX) and placed in a container . Co., Ltd.) for 60 minutes at 7000 rpm. In this way [Oil Phase 1] was prepared.

600 parts of water, 50 barrels [vinyl resin dispersion], 225 parts and 90 parts of a 48.5% aqueous solution of dodecyl sodium diphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical) were stirred and mixed. Industry Co., Ltd.). ethyl acetate fractions to obtain a milky white [aqueous phase 1].

0.2 part [ketimine compound] and 2000 parts [aqueous phase 1] were filled into a vessel containing [oil phase 1] and mixed at 13,000 rpm for 20 minutes using a TK HOMOMIXER. Thus [emulsion suspension 1] was prepared.

[Emulsion suspension 1] was filled into a vessel equipped with a stirrer and a thermometer and the solvent was removed at 30°C for 8 hours, followed by aging at 45°C for 4 hours. [Dispersion suspension 1] was thus prepared.

First, 100 parts [dispersion suspension 1] were filtered under reduced pressure. Then, 100 barrels of ion-exchange water was added to the filter cake, and it was filtered using the TK HOMOMIXER at 12,000 rpm for 10 minutes, and then filtered (this step will be referred to as "washing step (1) hereinafter). "). In addition, 100 parts of 10% aqueous sodium hydroxide solution was added to the filter cake, and after mixing at 12,000 rpm for 30 minutes with the TK HOMOMIXER, it was filtered under reduced pressure (hereinafter, this process is referred to as will call it the “washing process”). (hereinafter 2)"). Next, 100 parts of a 10% aqueous hydrochloric acid solution was added to the filter cake, mixed with TK HOMOMIXER at 12,000 rpm for 10 minutes, and then filtered (hereinafter 2). hereinafter, "washing step (3)"). Additional ion exchange was added to the filter cake. 300 parts of water were mixed at 12,000 rpm for 10 minutes using the TK HOMOMIXER and then filtered (this step is referred to below as "washing step (4)"). A series of washing processes (1) to (4) were repeated twice.

In addition, 100 parts of deionized water was added to the filter cake and mixed with the TK HOMOMIXER at 12,000 rpm for 10 minutes. The filter cake was then heated at 50°C for 4 hours and then filtered.

The filter cake was dried with a circulating air dryer at 45 °C for 48 hours and then sieved through a sieve with a pore size of 75 µm. Therefore, [Toner Mother Particle 1] was produced.

First, 100 barrels of [Toner Base Particle 1] were mixed with 2.0 parts of hydrophobized silica (HDK-2000, manufactured by Clariant AG) using a Henschel mixer and passed through a 500 mesh sieve. This is how [Toner 1] was prepared.

[Emulsion Tablet 2], [Dispersion Tablet 2] and [Toner Base Particle 2] were prepared in the same manner as in Example 1 to obtain [Toner 2] except that [Amorphous Polyester B-1] [Polyester amorphous B-2] in Example 1 was replaced.

[Emulsion Slurry 3], [Dispersion Slurry 3] and [Toner Base Particle 3] were prepared in the same manner as in Example 1 except that [Oil Phase 1] in Example 1 to obtain [Toner 3] 1 is replaced by [Oil Phase 3] described below.

Put 165 parts [wax dispersion], 165 parts [crystalline polyester dispersion], 180 barrels [amorphous B-3 polyester resin], 160 parts ethyl acetate, and 75 parts [color masterbatch] into the container. TK HOMOMIXER (manufactured by PRIMIX Co., Ltd.) was mixed at 7000 rpm for 60 minutes. In this way [Oil Phase 3] was prepared.

Fill the vessel with 170 parts [wax dispersion], 160 parts [crystalline polyester dispersion], 175 barrels [B-4 amorphous polyester resin], 155 parts ethyl acetate, and 75 parts [color masterbatch] TK HOMOMIXER ( manufactured by PRIMIX Co., Ltd.) was mixed at 7000 rpm for 60 minutes. [Oil Phase 4] was thus prepared.

First, 600 parts of water, 50 parts of [vinyl resin dispersion], 230 parts of 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical Industry Co., Ltd. .) and 90 parts of diethyl ether. The acetate was mixed with stirring. Thus milky white [aqueous phase 4] was produced.

Pour 0.2 part [ketimine compound], 2,000 parts [aqueous phase 4] and 50 parts [prepolymer A] into the vessel containing [oil phase 4] and mix for 20 minutes at 13,000 rpm with a TK HOMOMIXER. [Emulsion suspension 4] was thus prepared.

[Emulsion Slurry 4] was filled into a container equipped with a stirrer and a thermometer, dissolved at 30 °C for 8 hours, followed by aging at 45 °C for 4 hours, whereby [Dispersion Slurry 4] was prepared.

The [dispersion suspension 4] obtained was subjected to the same treatment as in Example 1. [Toner Base Particle 4] and [Toner 4] were thus prepared.

160 parts [wax dispersion], 165 parts [crystalline polyester dispersion], 160 parts ethyl acetate, 75 parts [masterbatch] and 190 parts [amorphous polyester resin B] were placed in a four-necked flask. -4], stirring to dissolve and disperse them. To this mixture, 10 parts of ethyl acetate, 45 parts of [prepolymer A] and 15 parts of 20% aqueous sodium hydroxide solution were added with stirring so that the neutralization rate can become 75%. [Oil Phase 5] was thus prepared.

100% Ethyl acetate was added to 1100 parts of deionized water based on a saturated solution amount, and 2% surfactant (sodium lauryl sulfate) was added based on an additional aqueous phase. Thus [aqueous phase 5] was prepared.

Gradually add [water phase 5] to [oil phase 5] for phase inversion and emulsification. Subsequently, the solvent is removed. Thus [emulsion suspension 5] was prepared.

1500 parts [emulsified suspension 5] and 1600 parts of deionized water were placed in a container and stirred for 5 minutes. Subsequently, 100 parts of a 20% aqueous magnesium sulfate solution were added dropwise to the mixture, further stirred for 5 minutes, and then heated to 60°C. Subsequently, 75 parts of a 20% aqueous magnesium sulfate solution were added dropwise to the mixture. After the diameter of the particles reached 5.0 µm, 350 parts of 20% aqueous sodium sulfate solution were added to the mixture to complete the aggregation process. This is how [the suspension of aggregates] was produced.

In this condition, the coagulated slurry was heated to 70°C with stirring, and once the particles had the desired roundness of 0.960, the slurry was cooled. [Dispersion suspension 5] was thus prepared.

[Dispersion slurry 5] was stored at 45°C for 10 hours, then filtered under reduced pressure, washed and dried as described below.

(1) Add 100 parts deionized water to the filter cake, use TK HOMOMIXER to mix (12000 rpm, 10 minutes) and filter.

(2) Add 900 parts deionized water to the filter cake in (1), use TK HOMOMIXER (12,000 rpm, 30 minutes) to vibrate and ultrasonically mix, and filter under reduced pressure. This operation was repeated until the electrical conductivity of the suspension liquid dropped below 10 μC/cm and then it was filtered. In this way a [filter cake] was prepared.

The filter cake was dried at 45 °C for 48 h with a circulating air dryer and then filtered through a sieve with a pore size of 75 μm. Therefore, [Toner Mother Particle 5] was produced.

Subsequently, 100 parts of [Toner Base Particle 5] and 2.0 parts of hydrophobized silica (HDK-2000, manufactured by Clariant AG) were mixed using a Henschel mixer and passed through a 500 mesh sieve. Thus [Toner 5] was prepared.

[Emulsion Slurry 6], [Dispersion Slurry 6], [Toner Base Particle 6], and [Toner 6] were made in the same manner as Example 1, except that [Amorphous Polyester B-1] Replace Example 1 with [ Amorphous Polyester B-5] .

[Emulsion Slurry 7], [Dispersion Slurry 7], [Toner Base Particle 7], and [Toner 7] were made in the same manner as Example 1, except that [Amorphous Polyester B-1] Replace Example 1 with [ Amorphous Polyester B-6] .

(fastness at high temperature)

Unfixed black still image at 0.6 mg/cm using the fixing unit for color multifunction device (IMAGIO MP C5503, manufactured by RICOH COMPANY, LTD.)²Formed on normal paper and fixed at different fixing temperatures. The temperature at which hot displacement occurs was measured and evaluated according to the following evaluation criteria.

[evaluation standard]

Excellent: 190°C or higher

Good: 180°C or more and less than 190°C.

General: above 170°C and below 180°C.

Malo: below 170°C.

(fix at low temperature)

Unfixed black still image at 0.6 mg/cm using the fixing unit for color multifunction device (IMAGIO MP C5503, manufactured by RICOH COMPANY, LTD.)²Formed on normal paper and fixed at different fixing temperatures. The temperature at which coagulation occurred was measured and scored according to the following evaluation criteria.

[evaluation standard]

Excellent: less than 120°C.

Good: 120°C or more and less than 125°C.

General: Above 125°C and below 130°C.

Bad: above 130°C

(heat resistant storage stability)

10 g of the toner was filled into a 100 ml glass bottle, allowed to stand at 50°C for 24 hours, and then evaluated according to the following evaluation criteria.

[evaluation standard]

Excellent: Shake the bottle 10 times, all the toner returns to its powder form

Good: Shake the bottle 10 times and half of the toner will return to its powdery state.

Normal: Shake the bottle 10 times, a small amount of toner will return to powder state

Bad: Shaking the bottle 10 times does not restore the toner to a powder state

(durability)

After the copy test of 100,000 sheets, the toner was removed from the developer by blowing, the mass of the remaining media was measured, and the mass was defined as "W1". This vehicle was then placed in toluene and the melt dissolved in toluene. After washing and drying the support, the mass of the support was measured and the mass was designated as "W2". Subsequently, the depletion rate was determined according to the following equation and evaluated according to the following evaluation criteria.

Spending rate (%)=[(W1−W2)/W1]×100[Evaluation criteria]

Excellent: 0% by weight to less than 0.01% by weight

Good: 0.01% by weight to less than 0.02% by weight

Generally: 0.02% by weight to less than 0.05% by weight

Defect: more than 0.05% by weight

Table 2 shows the evaluation results of toners in examples and comparative examples.

The binder resin refers to the sum of the prepolymer A, the amorphous polyester B and the crystalline polyester C.

Among the resins used in Examples and Comparative Examples, amorphous polyesters B-1 to B-5 are environmentally friendly resins.

Each of the amorphous polyester resins includes biomass-derived resins, recycled resins, and conventional petroleum-derived resins.

The above embodiments are examples and do not limit the present invention. Accordingly, many additional modifications and variations are possible in light of the above teachings. For example, elements and/or features of various illustrative embodiments may be combined with and/or substituted for one another within the scope of the invention.