Method for producing a toner

Abstract

Method for producing a toner containing an amorphous polyester, the toner production method comprising: a step of the melt kneading of amorphous polyesters 1 and 2, and a step of pulverizing the melt-kneaded composition, wherein the amorphous polyester 1 contains one of a tin compound and a titanium compound and the amorphous polyester 2 contains the other of a tin compound and a titanium compound, The Sn / Ti abundance ratio between Sn and Ti in the amorphous polyester, according to X-ray fluorescence analysis, is 20 / 80 to 80 / 20. a weight-averaged molecular weight Mw1 of the amorphous polyester 1 as measured by gel permeation chromatography (GPC) Mw1 < 7000, and a weight-averaged molecular weight Mw2 of the amorphous polyester 2 according to measurement by gel permeation chromatography (GPC) Mw2 < 7000.

Description

BACKGROUND OF THE INVENTION Area of ​​the invention

[0001] The present invention relates to a toner used in electrophotographic systems, electrostatic recording systems, electrostatic printing systems and toner jet systems. Description of the state of the art

[0002] The widespread adoption of full-color copiers using electrophotographic systems has led to a further increase in the need for high printing speeds and greater energy savings. A technique for accelerating toner melting during the fusing step was investigated to accommodate high-speed printing. Additionally, to achieve greater energy savings, a technique was explored to cause the toner to fuse at lower temperatures, thereby reducing power consumption during the fusing step.

[0003] Methods for accommodating high-speed printing and improving the low-temperature fixability of a toner involve reducing the glass transition temperature and / or softening point of the binder resin in the toner and using a binder resin exhibiting sharp melting properties. To provide sharp melting properties, investigations were carried out to use polyester resin as a binder resin and to reduce the molecular weight of the polyester resin. However, this resulted in a reduction of the hot offset resistance and / or the fixation circulation resistance. To overcome this problem, investigations were carried out regarding a toner using two species of binder resin, i.e., a high molecular weight resin and a low molecular weight resin.

[0004] For example, JP 2009-217053A discloses an electrostatic charge generation toner comprising at least two types of polyester resin, a colorant, and a release agent, for which a GSDp—a number-averaged particle size distribution index on the small-particle side—is within a specific range, and MwT and MwS satisfy a specific ratio, where D50T is a volume-averaged particle diameter of the entire toner, MwT is the weight-averaged molecular weight of the toner, and MwS is the weight-averaged molecular weight of the toner provided by classifying the toner into the volume-averaged particle diameter range of at least (1 / 5) x D50T and not more than (2 / 3) x D50T.

[0005] Additionally, JP 2008-281882A discloses a toner characteristically provided by emulsifying or dispersing and aggregating particles comprising at least polyester resin particles in an aqueous medium, wherein the polyester resin particles contain a polyester resin and the polyester resin is provided by the condensation of a carboxylic acid component containing a refined rosin and an alcohol component containing at least 65 mol% 1,2-propanediol in the divalent alcohol component, wherein the softening point of the polyester resin is at least 80°C and less than 120°C and the toner contains a coloring agent and a release agent.JP 2007-316212A relates to a binder resin for an electrostatically charged image development toner, comprising a non-crystalline polyester resin obtained by polycondensation of polycarboxylic acid and polyol, wherein the polyester resin contains structural units comprising substituted polycarboxylic acids with protic acid groups except for carboxyl groups, to 0.5 to 10 mol% in the total structural units; and wherein the tin and titanium concentrations in the polyester resin are both 100 ppm or less.

[0006] US 2007 / 218392 A1 relates to a toner containing a colorant and a binder resin, wherein the toner is produced by dissolving or dispersing a colorant, a precursor of the binder resin having a site capable of reacting with a compound containing an active hydrogen group, wherein the binder resin contains a modified polyester with an isocyanate-derived binding site; the tin content in the toner is 800 ppm or less; the content of a metal other than tin derived from a polyesterized catalyst is 10 ppm to 200 ppm; and the content of a metal other than tin derived from an isocyanate catalyst is 10 ppm to 200 ppm.

[0007] JP 2014-016551A relates to a binder resin for a toner, comprising: an amorphous polyester (A) obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing 5 to 25 mol of adipic acid, based on 100 mol of the alcohol component, in the presence of a non-Sn-C bonded tin catalyst and / or a titanium catalyst, and having a number-averaged molecular weight of 1000 to 2400, a weight-averaged molecular weight of 3000 to 6000, and a glass transition temperature of 38 to 48°C; and a crystalline polyester (B) obtained by condensation polymerization of an alcohol component containing 70 to 100 mol% of an aliphatic diol with 6 to 12 carbon atoms and a carboxylic acid component containing 70 to 100 mol% of an aliphatic A dicarboxylic acid compound containing 8 to 14 carbon atoms is obtained. SUMMARY OF THE INVENTION

[0008] In recent years, there has been a steadily increasing need for greater energy savings in copiers and for maximizing productivity by minimizing various copier settings. Regarding toner, there is also a need for a toner that enables fusing at lower temperatures, exhibits no hot offset or recirculation even at high temperatures, and has a wide fusing temperature range. A toner that meets these requirements has not yet been obtained under the given circumstances.

[0009] It is an object of the present invention to provide a toner that solves the aforementioned problems. More specifically, it is an object of the present invention to provide a toner that exhibits low-temperature fusing capability, excellent hot offset resistance, and excellent fuser circulation resistance.

[0010] The method for producing a toner of the present invention provides a toner containing an amorphous polyester, wherein the toner production method comprises: a step of melt kneading amorphous polyesters 1 and 2, and a step of pulverizing the melt kneaded composition, wherein the amorphous polyester 1 contains one of a tin compound and a titanium compound, and the amorphous polyester 2 contains the other of a tin compound and a titanium compound, wherein a Sn / Ti abundance ratio between Sn and Ti in the amorphous polyester, as determined by X-ray fluorescence analysis, is 20 / 80 to 80 / 20, a weight-averaged molecular weight Mw1 of the amorphous polyester 1, as determined by gel permeation chromatography (GPC), is < 7000, and a weight-averaged molecular weight Mw2 of the amorphous polyester 2, as determined by gel permeation chromatography (GPC), is < 7000.

[0011] The present invention can provide a toner that exhibits low-temperature fusing capability, excellent hot-offset resistance, and excellent fusing rotation resistance.

[0012] Further features of the present invention will become apparent from the following description of exemplary embodiments. DESCRIPTION OF THE EXECUTION FORMS

[0013] Unless otherwise specifically indicated, expressions such as "at least XX and not more than YY" and "XX to YY", which indicate numerical ranges, refer in the present invention to numerical ranges that include the lower and upper limits, which are the endpoints.

[0014] The method for producing a toner of the present invention provides a toner containing an amorphous polyester, wherein the toner production method comprises: a step of melt kneading amorphous polyesters 1 and 2, and a step of pulverizing the melt kneaded composition, wherein the amorphous polyester 1 contains one of a tin compound and a titanium compound, and the amorphous polyester 2 contains the other of a tin compound and a titanium compound, wherein a Sn / Ti abundance ratio between Sn and Ti in the amorphous polyester, as determined by X-ray fluorescence analysis, is 20 / 80 to 80 / 20, a weight-averaged molecular weight Mw1 of the amorphous polyester 1, as determined by gel permeation chromatography (GPC), is < 7000, and a weight-averaged molecular weight Mw2 of the amorphous polyester 2, as determined by gel permeation chromatography (GPC), is < 7000.

[0015] Investigations by the present inventors have shown that a low molecular weight component contained in the amorphous polyester is a factor reducing the hot offset and the fixation resistance. This low molecular weight component is a polyester component with a low degree of polymerization and a molecular weight of no more than approximately 2000, and its value tends to increase substantially when the weight-averaged molecular weight of the amorphous polyester is less than 7000. The adverse effects on the fixation property can be reduced by increasing the weight-averaged molecular weight of the amorphous polyester; however, this then leads to a reduction in the sharp melting property of the amorphous polyester resin.As a result of focused investigations, the present inventors discovered that by controlling the abundance ratio between the elements tin and titanium in the amorphous polyester resin within a specific range, the hot offset resistance and the curing resistance were improved, while the low-temperature curing properties remained unchanged. The present invention was obtained based on this finding. In the present invention, the amorphous polyester contains a tin compound and a titanium compound.

[0016] The mechanism by which the effects of the present invention are achieved is presumably obtained as follows. Tin compounds often have the ability to readily react with multiple carboxyl groups. Titanium compounds, on the other hand, often exhibit the ability to react with multiple hydroxyl groups. Moreover, it is frequently the case that much of the low molecular weight component of the amorphous polyester has the carboxyl group at one end and the hydroxyl group at the other. It is assumed that, by having a tin compound and a titanium compound both present in a certain ratio within the amorphous polyester, reactions occur during the toner manufacturing process between the low molecular weight component of the amorphous polyester and the tin and titanium compounds.

[0017] In these reactions, the carboxyl group at one end of the low molecular weight component of the amorphous polyester reacts with the tin compound, and the hydroxyl group at the other end reacts with the titanium compound. It is assumed that, because the tin compound and the titanium compound each have multiple reaction sites, an increase in molecular weight occurs through the successive crosslinking of the low molecular weight component of the amorphous polyester resin by the tin and titanium compounds. This is expected to result in a substantial improvement in hot offset resistance and fixation resistance.

[0018] It is assumed that these crosslinking reactions occur in the step in which heat is applied to the system, i.e., in the melt kneading step if the toner manufacturing process is a pulverization process, and in the aggregation or melting step for the dispersed particles if the toner manufacturing process is an aggregation process.

[0019] Additionally, if only the tin compound or only the titanium compound is present in the amorphous polyester, the increase in molecular weight cannot occur because the low molecular weight component in the amorphous polyester resin reacts only with one of the tin or titanium compounds. It is assumed that, as a result, the improvement in hot offset resistance and fixation resistance is not achieved.

[0020] The addition of this tin compound and this titanium compound as a catalyst for the synthesis of the amorphous polyester by condensation polymerization enables the tin compound and the titanium compound to be uniformly dispersed in the amorphous polyester and is therefore most preferred from the point of view of enabling the effective development of the crosslinking reactions during toner production. That is to say, the tin compound and the titanium compound are preferably derived from the catalysts used in the synthesis of the amorphous polyester.

[0021] Alternatively, an amorphous polyester containing a tin compound and a titanium compound can also be obtained by adding and mixing the tin compound and / or titanium compound after the amorphous polyester has already been produced.

[0022] Organotin compounds and inorganic tin compounds are preferred as tin compounds for use in the present invention. Specific examples are organotin compounds such as dibutyltin dichloride, dibutyltin oxide, and diphenyltin oxide. Here, an organotin compound denotes a compound containing the Sn-C bond.

[0023] Inorganic tin compounds lacking the Sn-C bond are also preferred for use. Here, an inorganic tin compound indicates a compound lacking the Sn-C bond. Examples of inorganic tin compounds include unbranched tin alkyl carboxylates, such as tin diacetate, tin dihexanoate, tin dioctanoate, and tin distearate; branched tin alkyl carboxylates, such as tin dineopentanoate and tin di(2-ethylhexanoate); tin carboxylates, such as tin oxalate; and dialkoxytin compounds, such as dioctyloxytin and distearoxytin. Among these tin compounds, tin alkyl carboxylates and dialkoxytin compounds are preferred, while tin alkyl carboxylates containing a carboxy group in the molecule, e.g., tin dioctanoate, tin di(2-ethylhexanoate), and tin distearate, are particularly preferred.

[0024] The aforementioned inorganic tin compounds exhibit multiple sites within each molecule that react with the carboxyl group. As a result, they are particularly well-suited to effectively promote the crosslinking reactions of the low molecular weight component of the amorphous polyester.

[0025] Titanium compounds that are preferred for use in the present invention can be, for example, titanium alkoxides, titanium aromatic carboxylate compounds and titanium compounds with a residue derived from alkanolamine.

[0026] The following compounds are provided as specific examples. Examples of titanium alkoxides include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetra(n-butyl) titanate, tetraoctyl titanate, and tetrastearyl titanate.

[0027] In addition, the crosslinking reaction with the hydroxy group in the low molecular weight component of the amorphous polyester also proceeds rapidly with titanium-aromatic carboxylate compounds, such as the following, and their use is therefore preferred.

[0028] Examples include titanium phthalate, titanium isophthalate, titanium terephthalate, titanium trimellitate, titanium pyromellitate, titanium 1,3-naphthalene dicarboxylate, titanium 2,4,6-naphthalene tricarboxylate and titanium salicylate.

[0029] The titanium-aromatic carboxylate compound is preferably the reaction product of an aromatic carboxylic acid and a titanium alkoxide. The aromatic carboxylic acid is more preferably at least a dibasic aromatic carboxylic acid (i.e., the aromatic carboxylic acid has at least two carboxyl groups) and / or an aromatic oxycarboxylic acid. The at least dibasic aromatic carboxylic acid can be, for example, a dicarboxylic acid, such as phthalic acid, isophthalic acid, and terephthalic acid and their anhydrides, and polybasic carboxylic acids, such as trimellitic acid, pyromellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, and naphthalenetetracarboxylic acid and their anhydrides and esters. The aforementioned aromatic oxycarboxylic acid can be, for example, salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, and tropic acid.Among the foregoing, the use of at least a dibasic carboxylic acid as the aromatic carboxylic acid is more preferred, while the use of isophthalic acid, terephthalic acid, trimellitic acid, and naphthalenedicarboxylic acid is particularly preferred.

[0030] Titanium compounds with an alkanolamine-derived residue in the molecule also exhibit high reactivity with the hydroxy group in the low molecular weight component of the polyester, and their use is therefore more preferred. Examples include titanium tetrakis(monoethanolaminate), titanium monohydroxytris(triethanolaminate), titanium dihydroxybis(triethanolaminate), titanium trihydroxytriethanolaminate, titanium dihydroxybis(diethanolaminate), titanium dihydroxybis(monoethanolaminate), titanium dihydroxybis(monopropanolaminate), titanium dihydroxybis(N-methyldiethanolaminate), titanium dihydroxybis(N-butyldiethanolaminate), the reaction product of tetrahydroxytitanium and N,N,N',N'-tetrahydroxyethylethylenediamine, titaniumylbis(triethanolaminate), titaniumylbis(diethanolaminate), titaniumylbis(monoethanolaminate), titaniumylhydroxytriethanolaminate, titaniumylisopropoxytriethanolaminate, and the intramolecular or intermolecular polycondensates of the aforementioned compounds.

[0031] These titanium compounds can be obtained stably, for example, by reacting a commercially available titanium dialkoxybis(alcoholaminate) (e.g., from DuPont) at 70°C to 90°C in the presence of water. The polycondensate can be obtained by further removing the water of condensation at 100°C by distillation under reduced pressure.

[0032] The following are more favored among these titanium compounds: titanium alkoxides, such as tetrapropyl titanate, tetraisopropyl titanate, tetra(n-butyl) titanate and tetraoctyl titanate; titanium aromatic carboxylate compounds, such as titanium isophthalate, titanium terephthalate, titanium trimellite and titanium pyromellite; and titanium dihydroxybis(triethanolaminate), titanium dihydroxybis(diethanolaminate), titanium monohydroxytris(triethanolaminate), titanium tetrakis(monoethanolaminate), titaniumylhydroxytriethanolaminate, titaniumylbis(triethanolaminate) and the intramolecular and intermolecular polycondensates of the foregoing.

[0033] The aforementioned titanium compounds exhibit multiple sites within each molecule that react with the hydroxyl group. As a result, they are particularly well-suited to effectively promote the crosslinking reactions of the low molecular weight component of the amorphous polyester.

[0034] It is critical for the present invention that the Sn / Ti abundance ratio of the elements tin and titanium in the amorphous polyester is between 20 / 80 and 80 / 20. If the Sn / Ti ratio is within this range, the crosslinking reactions of the low molecular weight component in the amorphous polyester proceed with good efficiency, resulting in molecules with extensive crosslinking structures and thus achieving the effects of the present invention. A ratio of 30 / 70 to 70 / 30 is more preferred from the perspective of improving charge stability and because it facilitates the development of the crosslinking reactions even more readily. Below 20 / 80 and above 80 / 20, the crosslinking reactions do not develop adequately, and the effects of the present invention cannot be achieved.

[0035] The following procedures are examples of methods for adjusting the Sn / Ti ratio. Amorphous polyester 1 can be produced using a tin compound as a catalyst, as described above, and amorphous polyester 2 can be produced using a titanium compound, as described above. Another example is modifying the mass ratio between amorphous polyester 1 and amorphous polyester 2, which are used in toner production.

[0036] Another example is to change the mass of the tin compound and / or titanium compound used as catalysts for the synthesis of the amorphous polyester.

[0037] Additionally, after the amorphous polyester has been produced using a tin compound or a titanium compound as described above, the other compound can be added and mixed to provide the Sn / Ti region of the present invention and thereby obtain an amorphous polyester containing a tin compound and a titanium compound.

[0038] The total abundance of tin and titanium in the amorphous polyester is preferably 50 to 20,000 ppm on a mass basis. At 50 ppm and above, the crosslinking reaction proceeds smoothly, and improvements in hot offset resistance and fixation resistance are readily achieved. Conversely, the loading performance is improved at 20,000 ppm and below. 200 to 5,000 ppm is more preferred.

[0039] The composition of the toner of the present invention is described in detail below. (Amorphous polyester)

[0040] Ordinary amorphous polyesters, constituted by an alcohol component and an acid component, can be used as the amorphous polyester, and examples of both components are provided below.

[0041] The alcohol component may be, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethylimethanol, butenediol, octenediol, cyclohexendimethylimethanol, hydrogenated bisphenol A, and bisphenol derivatives as specified by formula (1) below. Bisphenols, such as hydrogenated bisphenol A and the bisphenol derivatives specified by formula (1) below, and aromatic polyhydric alcohols, including 1,2-benzenedimethanol and 1,4-benzenedimethanol and their derivatives, are preferred, while bisphenols, such as hydrogenated bisphenol A and the bisphenol derivatives specified by formula (1) below, are more preferred.

[0042] [In the formula, R is an ethylene group or propylene group; x and y are each integers equal to or greater than 0; and the mean of x + y is 1 to 10.]

[0043] The alcohol component can also be, for example, polyhydric alcohols such as glycerin, pentaerythritol, sorbitol, sorbitan, and the oxyalkylene ethers of novolac-type phenolic resins.

[0044] On the other hand, the dibasic carboxylic acids that constitute the amorphous polyester can be, for example, benzenedicarboxylic acid and its derivatives, e.g., phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, and alkyldicarboxylic acids, e.g., succinic acid, adipic acid, sebacic acid, and azelaic acid and their anhydrides. Additional examples include succinic acid, which is formed by a C 6-18Alkyl or alkenyl group substituted, and anhydrides thereof, and unsaturated dicarboxylic acids, e.g., fumaric acid, maleic acid, citraconic acid, and itaconic acid, and their anhydrides. Other examples are polybasic carboxylic acids, e.g., trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, and benzophenonetetracarboxylic acid, and their anhydrides.

[0045] The amorphous polyester (preferably amorphous polyester 1 and more preferably amorphous polyesters 1 and 2) in the present invention is preferably the polycondensate of a carboxylic acid component and an alcohol component containing at least 80 mol% (more preferably at least 90 mol% and not more than 100 mol%) of an aromatic polyhydric alcohol (more preferably bisphenols). The inclusion of the alcohol component, which contains bisphenols as its main component, increases the reactivity with the titanium compound present in the amorphous polyester and further improves the fixation resistance.

[0046] An “alternative catalyst,” such as is commonly used in polyester production, can be employed to produce the aforementioned amorphous polyester. This could include, for example, a metal such as antimony, aluminum, manganese, nickel, zinc, lead, iron, magnesium, calcium, or germanium, or a compound containing such a metal. When this alternative catalyst is used alone, the aforementioned tin compound and titanium compound are used for toner production by their addition and mixing after the amorphous polyester has been produced.

[0047] In order to effectively express the crosslinking reactions mediated by the tin compound and the titanium compound, the tin compound and the titanium compound are preferably added at a minimum of 0.01 parts by mass and no more than 2 parts by mass per 100 parts by mass of the amorphous polyester. Furthermore, to enable a more reliable expression of the effects of the present invention, the addition of at least five times the amount by mass of the "other catalyst" used for the amorphous polyester production is preferred.

[0048] From the point of view of charging stability, the acid value of the amorphous polyester is preferably at least 1 mg KOH / g and not more than 40 mg KOH / g, and is more preferably at least 1 mg KOH / g and not more than 15 mg KOH / g.

[0049] The amorphous polyester characteristically comprises an amorphous polyester 1 whose weight-averaged molecular weight Mw1, as measured by gel permeation chromatography (GPC), is Mw1 < 7000.

[0050] Because the weight-averaged molecular weight Mw1 of the amorphous polyester 1 is < 7000 as measured by GPC, the toner exhibits a sharp melting property and is provided with excellent low-temperature fixability. Furthermore, the inclusion of a component with a relatively low molecular weight, not exceeding 2000, increases the molecular weight through reaction with and crosslinking by the tin and titanium compounds, resulting in a toner with excellent hot offset resistance and excellent fixative resistance. Low-temperature fixability decreases, and the coexistence between hot offset resistance and fixative resistance is significantly impaired, when Mw1 is at least 7000.

[0051] Additionally, Mw1 is at least 3000 from the perspective of toner storage capacity. A more preferred range for Mw1 is 3500 < Mw1 < 6500. Mw1 can be controlled, for example, by the amounts of alcohol and acid components introduced during production, the reaction temperature, and the reaction time.

[0052] The glass transition temperature of the amorphous polyester 1 is preferably at least 40°C and not more than 65°C, taking into account the aspect of the coexistence of toner storage capacity with low-temperature fixability, and is more preferably at least 50°C and not more than 60°C.

[0053] The softening point of the amorphous polyester 1 is preferably at least 75°C and not more than 120°C, taking into account the aspect of the coexistence of toner storage capacity with low-temperature fixability.

[0054] The amorphous polyester used in the toner of the present invention comprises an amorphous polyester 2 in addition to the amorphous polyester 1.

[0055] The hot offset resistance and the fixation resistance are further improved by ensuring that the weight-averaged molecular weight Mw2 of the amorphous polyester 2, as measured by gel permeation chromatography (GPC), is < 7000. A preferred range for Mw2 is 3500 < 6500. Mw2 can be controlled, for example, by the amounts of alcohol and acid components added during production, the reaction temperature, and the reaction time.

[0056] The amorphous polyesters 1 and 2 preferably contain at least a selection of tin compounds and titanium compounds. For example, amorphous polyester 1 preferably contains a titanium compound and amorphous polyester 2 contains a tin compound.

[0057] The amorphous polyester used in the toner of the present invention may contain additional amorphous polyester besides the amorphous polyester 1 and the amorphous polyester 2.

[0058] The proportion of the amorphous polyester 1, which has a weight-averaged molecular weight Mw by GPC of less than 7000, is preferably at least 50 parts by mass per 100 parts by mass of the total amorphous polyester, because this provides a large amount of low molecular weight component in the amorphous polyester and the crosslinking reaction progresses further. (Other binder resin)

[0059] The toner of the present invention contains amorphous polyester as the binder resin. With the aim of improving the dispersibility of the pigment and improving the charging stability and blocking resistance of the toner, an "other resin" as described below can also be added, in addition to the aforementioned amorphous polyester, in an amount that does not impair the effects of the present invention.

[0060] Examples of this “other resin” include: homopolymers of styrene and their derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene copolymers, such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate ester copolymer, styrene-methacrylate ester copolymer, styrene-methyl-a-chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; as well as polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarin indole resins and petroleum resins. (dye)

[0061] A colorant can be used in the toner of the present invention. This colorant can be, for example, the following.

[0062] The black colorant can be, for example, carbon black, or black colorants produced by mixing a yellow, magenta, and cyan colorants to achieve black. While a single pigment can be used for the colorant, the simultaneous use of a dye and a pigment is more advantageous for improving the brilliance of full-color images.

[0063] Examples of pigments for magenta toners include: CI 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 and 282; CI Pigment Violet 19; and CI Vat Red 1, 2, 10, 13, 15, 23, 29 and 35.

[0064] Examples of dyes for magenta toners include: oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109 and 121, CI Disperse Red 9, CI Solvent Violet 8, 13, 14, 21 and 27, and CI Disperse Violet 1; and basic colors, such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39 and 40 and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 and 28.

[0065] Examples of pigments for cyanotones include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16 and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments with at least 1 and not more than 5 phthaloimidomethyl groups substituted on the phthalocyanine backbone. CI Solvent Blue 70 is an example of a cyanotone dye.

[0066] Examples of pigments for yellow toners include: CI 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 and 185; and CI Vat Yellow 1, 3 and 20. CI Solvent Yellow 162 is an example of a dye for yellow toner.

[0067] The colorant content is preferably at least 0.1 parts by mass and not more than 30 parts by mass per 100 parts by mass of the binder resin. The binder resin here refers to the sum of the amorphous polyester and the aforementioned "other resins". (Wax)

[0068] A wax can be used in the toner of the present invention. This wax can be, for example, the following: hydrocarbon waxes, such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch waxes; oxides of hydrocarbon waxes, such as oxidized polyethylene wax and their block copolymers; waxes in which the main component is fatty acid esters, such as carnauba wax; and waxes provided by partial or complete deacidification of fatty acid esters, such as deacidified carnauba wax.

[0069] Additional examples include: saturated straight-chain fatty acids, such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids, such as brassic acid, eleostearic acid, and parinaric acid; saturated alcohols, such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols, such as sorbitol; esters between fatty acids, such as palmitic acid, stearic acid, behenic acid, and montanic acid, and alcohols, such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides, such as linoleamide, oleamide, and lauramide; saturated fatty acid bisamides, such as methylenebisstearamide, ethylenebiscapramide, ethylenebislauramide, and hexamethylenebisstearamide; unsaturated fatty acid amides, such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyladipamide and N,N'-dioleylsebacamide;Aromatic bisamides, such as m-xylenebisstearamide and N,N'-distearylisophthalamide; fatty acid metal salts (commonly known as metal soaps), such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes provided by grafting an aliphatic hydrocarbon wax using a vinylic monomer, such as styrene or acrylic acid; partial esters between a polyhydric alcohol and a fatty acid, such as behen monoglyceride; and hydroxy-group-containing methyl ester compounds obtained by hydrogenation of vegetable oils.

[0070] Among these waxes, hydrocarbon waxes, such as paraffin waxes and Fischer-Tropsch waxes, and fatty acid ester waxes, such as carnauba wax, are preferred with regard to further improving hot offset resistance. With regard to further improving hot offset resistance, hydrocarbon waxes are more strongly preferred in the present invention, and Fischer-Tropsch waxes are even more strongly preferred.

[0071] The wax content is preferably at least 1 part by mass and not more than 20 parts by mass per 100 parts by mass of the binder resin.

[0072] The peak temperature of the maximum endothermic peak of the wax in an endothermic curve, measured during the rise using a differential scanning calorimeter (DSC), is preferably at least 45°C and not more than 140°C, and more preferably at least 70°C and not more than 105°C. Toner retention can coexist with the hot offset resistance if the peak temperature of the maximum endothermic peak of the wax is within the indicated range, which is therefore preferred. (Load control device)

[0073] A charge control agent can, if necessary, also be incorporated into the toner of the present invention. While a known charge control agent can be used as the charge control agent incorporated into the toner, it is particularly preferred that it be a metallic compound of an aromatic carboxylic acid which is colorless, supports a rapid charging rate of the toner and stably maintains a certain charge quantity.

[0074] Examples of negative charge-controlling agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds with sulfonic acid or carboxylic acid in a side-chain position, polymeric compounds with sulfonate salts or sulfonate esters in a side-chain position, polymeric compounds with carboxylate salts or carboxylate esters in a side-chain position, boron compounds, urea compounds, silicon compounds, and calixarenes. Examples of positive charge-controlling agents include quaternary ammonium salts, polymeric compounds with a quaternary ammonium salt in a side-chain position, guanidine compounds, and imidazole compounds. The charge-controlling agent can be added internally to the toner particles or externally. The amount of charge-controlling agent added is preferably 0.2 parts by mass and not more than 10 parts by mass per 100 parts by mass of the binder resin. (Inorganic fine powder)

[0075] An additional inorganic fine powder can be included in the toner of the present invention, if necessary. The inorganic fine powder can be added internally to the toner particle or can be mixed with the toner particle as an external additive. Inorganic fine powders, such as silica, titanium dioxide, and aluminum oxide, are preferred as external additives. The inorganic fine powder is preferably made hydrophobic using a hydrophobizing agent, such as a silane compound, silicone oil, or a mixture thereof.

[0076] An inorganic fine powder with a specific surface area of ​​at least 50 m² 2 / g and no more than 400 m 2 / g is preferred as an external additive to improve flowability, whereas an inorganic fine powder with a specific surface area of ​​at least 10 m² 2 / g and no more than 50m 2 / g is preferred for stabilizing shelf life. Combinations of inorganic fine powders with specific surface areas in the indicated regions can be used to balance flowability with shelf-life stabilization.

[0077] The external additive is preferably used at a concentration of at least 0.1 parts by mass and no more than 10.0 parts by mass per 100 parts by mass of the toner particle. Mixing the toner particle with an external additive can utilize a known mixer, such as a Henschel mixer. <Developer>

[0078] The toner of the present invention can be used as a one-component developer, but its use mixed with a magnetic carrier as a two-component developer is preferred in order to produce additional improvements in dot reproducibility and also from the point of view of obtaining a stable image on a long-term basis.

[0079] A generally known magnetic support can be used, for example, surface-oxidized iron powder and non-oxidized iron powder; metal particles, such as those of iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium and rare earths and their alloying particles and oxide particles; magnetic bodies, such as ferrite; and magnetic body-dispersed resin supports (known as resin supports) which contain a magnetic body and a binder resin that maintains this magnetic body in a dispersed state.

[0080] When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, very good effects are obtained when the carrier mixing ratio, expressed as the toner concentration in the two-component developer, is preferably at least 2% by mass and not more than 15% by mass, and more preferably at least 4% by mass and not more than 13% by mass. <herstellungsverfahren>

[0081] A dry process, namely a pulverization process, is used as the method for producing the toner particle.

[0082] Regardless of the method, the tin compound and titanium compound contained in the amorphous polyester and the low molecular weight component are preferably mixed in the amorphous polyester, and a step is carried out in which the amorphous polyester 1 is heated. In this heating step, the heating is preferably carried out to at least the glass transition temperature of the amorphous polyester 1 and more preferably to a temperature that is at least the softening point of the amorphous polyester 1. This allows the crosslinking reactions of the low molecular weight component, the tin compound, and the titanium compound in the amorphous polyester 1 to develop efficiently, and the effects of the present invention can then be expressed more reliably.

[0083] In the case of the pulverization process, this can be achieved in the step of melt kneading the amorphous polyester.

[0084] In a pulverization process that includes a melt kneading step of the amorphous polyester, it is easy to apply high shear forces while maintaining high temperatures. This facilitates more extensive development of the tin- and titanium-mediated crosslinking reactions of the low-molecular-weight component of the amorphous polyester, thereby enabling further improvements in hot-offset resistance and fixation resistance, and is therefore utilized.

[0085] An example of a toner manufacturing process using a pulverization process is described below.

[0086] In a starting material mixing step, the materials that constitute the toner particles, for example, the amorphous polyester and optionally other components such as other resins, wax, colorants, and charge control agents, are weighed out in specific quantities and blended and mixed. The mixing apparatus can be, for example, a double-cone mixer, V-mixer, roller mixer, super mixer, Henschel mixer, Nauta mixer, or Mechano Hybrid (Nippon Coke & Engineering Co., Ltd.).

[0087] The mixed materials are then melt-kneaded to disperse the wax and other components in the amorphous polyester. The kneading outlet temperature can be adjusted as appropriate depending on the amorphous polyester used, but 100°C to 180°C is usually preferred. A batch kneader, such as a pressure kneader and Banbury mixer, or a continuous kneader can be used in this melt-kneading step, and single-screw and twin-screw extruders are mainstream because they offer the advantage of enabling continuous production.

[0088] Examples include the KTK twin-screw extruder (Kobe Steel, Ltd.), TEM twin-screw extruder (Toshiba Machine Co., Ltd.), PCM kneader (Ikegai Corp), twin-screw extruder (KCK), co-kneader (Buss AG), and Kneadex (Nippon Coke & Engineering Co., Ltd.). Additionally, the resin composition produced by melt kneading can be rolled out using, for example, a two-roll mill and cooled in a cooling step using, for example, water.

[0089] The cooled resin composition is then pulverized to the desired particle diameter in a pulverization step. This step can involve coarse pulverization using a grinding mill, such as a crusher, hammer mill, or spring mill, followed by fine pulverization using a pulverizer, such as the Kryptron System (Kawasaki Heavy Industries, Ltd.), Super Rotor (Nisshin Engineering Inc.), or Turbo Mill (Freund-Turbo Corporation), or using an air jet system.

[0090] A classified product (toner particles) is then obtained as desired by performing classification using a sieve or classifier, e.g., an internal classifier such as Elbow Jet (Nittetsu Mining Co., Ltd.), or a centrifugal classifier such as Turboplex (Hosokawa Micron Corporation), TSP Separator (Hosokawa Micron Corporation), or Faculty (Hosokawa Micron Corporation). Of the aforementioned, Faculty (Hosokawa Micron Corporation) can perform a spherization treatment of the toner particles simultaneously with classification and is therefore preferred from the perspective of improving transfer efficiency.

[0091] After pulverization, the toner particle can, if necessary, be subjected to a surface treatment, such as a spherization treatment, using Hybridization System (Nara Machinery Co., Ltd.), Mechanofusion System (Hosokawa Micron Corporation), Faculty (Hosokawa Micron Corporation) or Meteo Rainbow MR-type (Nippon Pneumatic Mfg. Co., Ltd.).

[0092] The average circularity of the toner, from the perspective of exhibiting cleaning performance in coexistence with improved transferability, is preferably at least 0.930 and not more than 0.985. If the toner is produced by a pulverization process, a surface treatment, e.g., a spherization treatment or heat treatment, is preferably applied to the toner particle to produce a toner with the indicated average circularity.

[0093] If necessary, the surface of the toner particle can be subjected to an additional external addition treatment with an external additive. The method for performing the external addition treatment with the external additive can, for example, involve mixing a specific quantity of any of several known external additives with the classified toner, and stirring and mixing using a mixing device as the external addition device, such as a double-cone mixer, V-mixer, roller mixer, supermixer, Henschel mixer, Nauta mixer, and Mechano Hybrid (Nippon Coke & Engineering Co., Ltd.) or Nobilta (Hosokawa Micron Corporation).

[0094] The methods used to measure the various properties of the toner and the starting materials are described below. <Sn / Ti Abundanzverhältnis durch Röntgenfluoreszenzanalyse von dem Sn und Ti, die in dem amorphen Polyester vorhanden sind>

[0095] The Sn / Ti abundance ratio is determined by X-ray fluorescence. The X-ray fluorescence is measured according to JIS K 0119-1969 and is specific as follows.

[0096] The following is used as the measuring instrumentation: an Axios (PANalytical BV) wavelength-dispersive X-ray fluorescence analyzer and the SuperQ ver. 4.0F (PANalytical BV) software supplied with it for setting the measurement conditions and analyzing the measurement data. Rh is used for the anode of the X-ray tube; a vacuum is used for the measurement atmosphere; 27 mm is used for the measurement diameter (collimator mask diameter); and 10 seconds is used for the measurement time. A known detector, e.g., a proportional counter (PC) and a scintillation counter (SC), can be used for the detector.

[0097] 4 g of the sample is inserted into the designated aluminium press ring and smoothed, and formed into a pellet with a thickness of 2 mm and a diameter of 39 mm by compression for 60 seconds at 20 MPa using a “BRE-32” tablet compression forming machine (Maekawa Testing Machine Mfg. Co., Ltd.) to produce a pellet that is used as the measurement sample.

[0098] Samples for constructing the calibration curves are first prepared. A known quantity of tin oxide is added and mixed with 100 parts by mass of a styrene powder that contains neither tin nor titanium, followed by the preparation of the pellet for the tin element. Similarly, a known quantity of titanium oxide is added and mixed with 100 parts by mass of a styrene powder that contains neither tin nor titanium, followed by the preparation of the measuring pellet for the titanium element.

[0099] Each of the manufactured pellets is measured with the X-ray fluorescence analyzer and calibration curves are constructed for tin and titanium from the peak intensities obtained from the individual samples of tin oxide or titanium oxide in the styrene powder.

[0100] A sample of the amorphous polyester used in the present invention is then measured with the X-ray fluorescence analyzer, and the tin and titanium content are determined by comparing the obtained peak intensities with the calibration curves, and the resulting values ​​are used to determine the Sn / Ti abundance ratio for Sn and Ti.

[0101] When a plurality of amorphous polyesters are used, the tin content and titanium content are determined for each amorphous polyester used, and the Sn / Ti content of the amorphous polyester is calculated from the content proportions of the plurality of amorphous polyesters. <Verfahren zum Messung des gewichtsgemittelten Molekulargewichts (Mw) durch GPC>

[0102] The weight-averaged molecular weight (Mw) is measured using gel permeation chromatography (GPC) as follows.

[0103] First, the sample (resin) is dissolved in tetrahydrofuran (THF) for 24 hours at room temperature. The resulting solution is filtered through a solvent-resistant membrane filter with a pore diameter of 0.2 µm (Tosoh Corporation) to obtain a sample solution. The sample solution is adjusted so that the concentration of a THF-soluble component is approximately 0.8 wt%. The measurement is then performed using this sample solution under the following conditions. Instrument: HLC8120 GPC (Detector: RI) (Tosoh Corporation) Columns: 7-column pulley from Shodex KF-801, 802, 803, 804, 805, 806 and 807 (Showa Denko Kabushiki Kaisha) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / minute Oven temperature: 40.0°C Sample injection volume: 0.10 mL

[0104] A molecular weight calibration curve, created using polystyrene resin standards (for example, 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 and A-500”, Tosoh Corporation), is used to determine the molecular weight of the sample. <Verfahren zum Messen des Erweichungspunktes der Harze>

[0105] The softening point of the resins is measured according to the operating instructions provided with the instrument using a "Flowtester CFT-500D Flow Property Evaluation Instrument" (Shimadzu Corporation), which is a constant-load extrusion-type capillary rheometer. With this instrument, while a constant load is applied by a piston from above the sample, the sample, which is filled into a cylinder, is heated and melted, and the molten sample is extruded from a nozzle at the bottom of the cylinder; a flow curve showing the relationship between the piston stroke and the temperature is obtained.

[0106] The "melting temperature by the 1 / 2 method," as described in the operating instructions accompanying the device shown, is used in the present invention as the softening point. The melting temperature using the 1 / 2 method is determined as follows. First, the value of X—that is, 1 / 2 of the difference between Smax, which is the piston stroke at the completion of the outflow, and Smin, which is the piston stroke at the beginning of the outflow—is determined (X = (Smax - Smin) / 2). The temperature of the flow curve when the piston stroke reaches "Smin + X" in the flow curve is the melting temperature determined by the 1 / 2 method.

[0107] The test sample is prepared by subjecting approximately 1.0 g of the resin to compression molding for approximately 60 seconds at approximately 10 MPa in a 25°C environment using a tablet compression molding machine (e.g. NT-100H, NPa System Co., Ltd.) to provide a cylindrical shape with a diameter of approximately 8 mm.

[0108] The measurement conditions with the CFT-500D are as follows. Test mode: Temperature rise method Starting temperature: 50°C Saturated temperature: 200°C Measurement interval: 1.0°C Rate of increase: 4.0°C / minute Piston cross-sectional area: 1,000 cm² 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Nozzle opening diameter: 1.0 mm Nozzle length: 1.0 mm <Verfahren zum Messen des Säurewerts der Harze>

[0109] The acidity of the polyester resin is measured using the following method. The acidity is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acidity of the polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure. (1) Preparation of reagent

[0110] A phenolphthalein solution is obtained by dissolving 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and adjusting to 100 mL by adding ion-exchange water. 7 g of high-purity potassium hydroxide are dissolved in 5 mL of deionized water and made up to 1 L by adding ethyl alcohol (95% by volume). This is placed in an alkali-resistant container, avoiding contact with, for example, carbon dioxide, and left to stand for 3 days. The mixture is then filtered to obtain a potassium hydroxide solution. The potassium hydroxide solution is stored in an alkali-resistant container. The ratio of this potassium hydroxide solution is determined by the amount of potassium hydroxide required for neutralization when 25 mL of a 0.1 mol / L hydrochloric acid solution is placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution are added, and a titration is performed using the potassium hydroxide solution.The 0.1 mol / L hydrochloric acid solution used is prepared according to JIS K 8001-1998. (2) Procedure(A) Main test

[0111] 2.0 g of a sample of the powdered polyester resin are weighed precisely into a 200 mL Erlenmeyer flask, and 100 mL of a toluene:ethanol (2:1) solution are added. Dissolution is carried out for 5 hours. A few drops of the previously mentioned phenolphthalein solution are added as an indicator, and titration is performed using the previously mentioned potassium hydroxide solution. The titration is complete when the pale pink color of the indicator persists for 30 seconds. (B) Blind test

[0112] The same titration as the above procedure is performed, but without the use of the sample (i.e., only with the toluene:ethanol (2:1) mixed solution).

[0113] (3) The acid value is calculated by substituting the results obtained into the following equation: A=[(C−B)×f×5.61] / S Here, A: acidity value (mg / KOH / g); B: amount (mL) of potassium hydroxide solution added to the blank test; C: amount (mL) of potassium hydroxide solution added to the main test; f: potassium hydroxide solution factor; and S: sample (g). <Verfahren zum Messen der Glasübergangstemperatur (Tg) der Harze>

[0114] The glass transition temperature (Tg) of the resins is measured based on ASTM D 3418-82 using a Q1000 dynamic differential calorimeter (TA Instruments). Temperature correction in the instrument detection section is performed using the melting points of indium and zinc, and the heat quantity is corrected using the heat of fusion of indium.

[0115] Specifically, approximately 5 mg of the resin are weighed out precisely and placed in an aluminum crucible. Using an empty aluminum crucible as a reference, the measurement is performed at a temperature increase rate of 10°C / minute within the measurement temperature range of 30°C to 200°C. The measurement is carried out by initially raising the resin temperature to 200°C, holding it for 10 minutes, then cooling it to 30°C, and subsequently reheating it. The change in specific heat within the temperature range of 35°C to 100°C during this second heating step is recorded. The glass transition temperature (°C) of the resin is determined by the point at the intersection of the dynamic heat curve and the midpoint of the baseline before and after the change in specific heat occurs. <Verfahren zum Messen der Peaktemperatur des maximalen endothermen Peaks der Wachse>

[0116] The peak temperature of the maximum endothermic peak of the waxes is measured based on ASTM D 3418-82 using a Q1000 dynamic differential calorimeter (TA Instruments). Temperature correction in the instrument detection section is performed using the melting points of indium and zinc, and the heat quantity is corrected using the latent heat of fusion of indium.

[0117] Specifically, approximately 10 mg of wax are weighed out precisely and placed in an aluminum crucible. Using an empty aluminum crucible as a reference, the measurement is performed at a temperature increase rate of 10°C / minute within the measurement temperature range of 30°C to 200°C. The measurement is carried out by initially raising the temperature of the wax to 200°C, holding it for 10 minutes, then cooling it to 30°C, and subsequently reheating it. The peak temperature of the maximum endothermic peak of the wax is taken as the temperature shown in the DCS curve within the 30°C to 100°C temperature range during this second heating step. <Messung der BET spezifischen Oberfläche des anorganischen Feinpulvers>

[0118] The BET specific surface area of ​​the inorganic fine powder is measured based on JIS Z 8830 (2001). The specific measurement procedure is as follows.

[0119] A TriStar 3000 Automatic Specific Surface Area Porosimetry Analyzer (Shimadzu Corporation), which uses gas adsorption via a constant volume method as its measuring principle, is used as the measuring instrument. The measurement conditions are set, and the measurement data are analyzed using TriStar 3000 Version 4.00, the software provided with this instrument. A vacuum pump, a nitrogen gas line, and a helium gas line are connected to this instrument. The value calculated using a multi-point BET method and nitrogen gas as the adsorption gas is used as the BET specific surface area of ​​the inorganic fine powders in the present invention.

[0120] The BET specific surface area is calculated as follows.

[0121] First, nitrogen gas is adsorbed onto the inorganic fine powder, and the equilibrium pressure P (Pa) within the sample cell and the amount of nitrogen adsorption Va (mol / g) by the external additive are measured. The adsorption isotherm is obtained using the relative pressure Pr—which is the value obtained by dividing the equilibrium pressure P (Pa) within the sample cell by the saturation vapor pressure of nitrogen Po (Pa)—for the horizontal axis and the amount of nitrogen adsorption Va (mol / g) for the vertical axis. The monomolecular layer adsorption amount Vm (mol / g), which is the amount of adsorption required to form a monomolecular layer on the surface of the external additive, is then determined using the BET equation provided below. Pr / Va(1−Pr)=1 / (Vm×C)+(C−1)×Pr / (Vm×C)

[0122] Here, C is the BET parameter and is a variable that changes with the type of sample, the type of adsorption gas, and the adsorption temperature.

[0123] The BET equation can be represented as a straight line with a slope of (C - 1) / (Vm x C) and an intersection point of 1 / (Vm x C), by using Pr for the x-axis and Pr / Va (1 - Pr) for the y-axis. This straight line is called the BET representation. Slope of the straight line = (C−1) / (Vm×C) Intersection of the straight line = 1 / (Vm×C)

[0124] The slope of this straight line and the value of its intersection point can be calculated by plotting the measured values ​​of Pr and the measured values ​​of Pr / Va (1 - PR) on a graph and generating a straight line using the method of least squares. Vm and C can be calculated by substituting these values ​​into the aforementioned equations and solving the resulting simultaneous equations.

[0125] The BET specific surface area S (m2 / g) of the inorganic fine powder is then calculated using the following equation and the Vm calculated as above and the molecular cross-sectional area of ​​the nitrogen molecule (0.162 nm). 2 ) calculated S=Vm×N×0.162×10−18

[0126] Here, N is Avogadro's number (mol). -1 ).

[0127] Measurements using this device are performed using the “TriStar 3000 Operating Manual V4,0” which is provided with the device, and are specifically carried out using the following procedure.

[0128] The glass sample cell (shaft diameter = 3 / 8 inch, volume = approximately 5 mL) provided with the instrument is carefully cleaned and dried, then weighed precisely to determine its tare weight. Approximately 0.1 g of the external additive is introduced into this sample cell using a funnel.

[0129] The sample cell loaded with the inorganic fine powder is placed in a "Vacuprep 061 Pretreatment Apparatus" (Shimadzu Corporation), which is connected to a vacuum pump and a nitrogen gas line. Vacuum degassing is then carried out for approximately 10 hours at 23°C. This vacuum degassing is performed by incremental degassing while the valve is adjusted to prevent inorganic fine powder from being drawn into the vacuum pump. The pressure in the sample cell decreases gradually as the degassing process progresses, eventually reaching approximately 0.4 Pa (about 3 millitorr). After vacuum degassing is complete, nitrogen gas is gradually introduced into the sample cell, the interior of the sample cell is returned to atmospheric pressure, and the sample cell is removed from the pretreatment apparatus.The mass of this sample cell is weighed precisely, and the exact mass of the external additive is calculated from the difference between this weight and the tare weight. The sample cell is sealed with a rubber stopper during weighing to prevent the external additive from being contaminated by, for example, atmospheric moisture.

[0130] The isothermal jacket, provided with the instrument, is then placed on the stem of the sample cell, which is loaded with the inorganic fine powder. The rod electrode, also provided with the instrument, is inserted into the sample cell, and the sample cell is then inserted into the instrument's analysis port. This isothermal jacket is a cylindrical element with a porous inner surface and an impermeable outer surface, and it draws liquid nitrogen to a specific level through capillary action.

[0131] The free space within the sample cell, including the connection ports, is then measured. To determine this free space, the volume of the sample cell at 23°C is measured using helium gas. Then, after the sample cell has been cooled with liquid nitrogen, the volume is measured again using helium gas. The free space is then calculated by converting this difference into the measured volume. Additionally, the saturation vapor pressure Po (Pa) of nitrogen is automatically measured separately using the Po tube integrated into the instrument.

[0132] Then, after the interior of the sample cell has been vacuum degassed, the sample cell is cooled with liquid nitrogen while vacuum degassing continues. The nitrogen gas is then introduced into the sample cell in two stages, and the nitrogen molecules adsorb onto the inorganic fine powder. At this point, the adsorption isotherm described above is obtained by measuring the equilibrium pressure P (Pa), as required, and this adsorption isotherm is converted into a BET plot. The relative pressure Pr points for data collection are set to a total of six points: 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is generated from the obtained measurement data using the least squares method, and Vm is calculated from the slope and the intersection point of this straight line. Using this value of Vm, the BET-specific surface area of ​​the inorganic fine powder is calculated as described above. <Gewichtsgemittelter Teilchendurchmessers (D4) von dem Tonerteilchen>

[0133] Using a “Coulter Counter Multisizer 3” (registered trademark, Beckman Coulter), a precision particle size distribution measuring instrument which operates a pore electrical resistance method and is equipped with a 100 µm aperture tube, and the accompanying intended software, i.e. “Beckman Coulter Multisizer 3 Version 3.51” (Beckman Coulter Inc.), for setting the measurement conditions and analyzing the measurement data, the weight-averaged particle diameter (D4) of the magnetic toner is determined by performing the measurement with 25000 channels for the number of effective measurement channels and analyzing the measurement data.

[0134] The aqueous electrolyte used for the measurements is prepared by dissolving a high-purity sodium chloride in deionized water to provide a concentration of approximately 1 wt%, and ISOTON II (Beckman Coulter, Inc.) can be used, for example.

[0135] The intended software is configured as follows before measurement and analysis.

[0136] In the "Modify the standard operating method (SOM)" window of the intended software, the total number of measurements in control mode is set to 50,000 particles; the number of measurements is set to 1; and the Kd value is set to a value obtained using "Standard Particle 10.0 µm" (Beckman Coulter, Inc.). The threshold and noise level are set automatically by pressing the threshold / noise level measurement button. Additionally, the current is set to 1600 µA; the gain is set to 2; the electrolyte is set to Isotonic II; and the aperture tube purge after measurement is selected.

[0137] In the “setting conversion from pulses to particle diameter” window of the intended software, the bin interval is set to logarithmic particle diameter; the particle diameter bin is set to 256 particle diameter bin; and the particle diameter range is set to at least 2 µm to no more than 60 µm.

[0138] The specific measurement procedure is as follows. (1) Approximately 200 mL of the aqueous electrolyte solution described above are introduced into a Multisizer 3-specific 250 mL round-bottomed beaker, which is then placed in the sample stand and stirred counterclockwise with a stirring rod at 24 revolutions per second. Any dirt and air bubbles within the aperture tube are removed beforehand using the "Aperture Flush" function of the designated software. (2) Approximately 30 mL of the aqueous electrolyte solution described above are introduced into a 100 mL flat-bottomed beaker. To this, approximately 0.3 mL of a dilution prepared by triple dilution (by mass) of “Contaminon N” (a 10 wt% aqueous solution of a neutral pH 7 detergent for cleaning precision measuring instruments, containing a non-ionic surfactant, an anionic surfactant and an organic framework substance, manufactured by Wako Pure Chemical Industries) is added as a dispersant. (3) A certain quantity of deionized water is introduced into a water tank of an ultrasonic dispersion system Tetora 150 (Nikkaki Bios Co. Ltd.), which is an ultrasonic disperser with an electrical power of 120 W and equipped with two oscillators (oscillation frequency = 50 kHz) whose phases are offset by 180°, and approximately 2 mL of Contaminon N are added to this water tank. (4) The beaker described in (2) is inserted into the beaker holder opening of the ultrasonic disperser and the ultrasonic disperser is started. The vertical position of the beaker is adjusted such that the resonance condition of the surface of the aqueous electrolyte solution inside the beaker is maximized. (5) While the aqueous electrolyte solution within the beaker set up according to (4) is being ultrasonically irradiated, approximately 10 mg of the toner is added to the aqueous electrolyte solution in small portions and dispersed. The ultrasonic dispersion treatment is continued for a further 60 seconds. The water temperature in the water tank is controlled as needed during the ultrasonic dispersion to be at least 10°C and not more than 40°C. (6) Using a pipette, the dispersed toner-containing aqueous electrolyte solution prepared in (5) is added dropwise to the round-bottomed beaker, which is inserted into the sample stand as described in (1), to adjust the measurement concentration to approximately 5%. The measurement is then carried out until the number of measured particles reaches 50,000. (7) The measurement data are analyzed by the previously displayed intended-use software supplied with the device, and the weight-averaged particle diameter (D4) is calculated. If Graph / Vol-% is selected within the intended-use software, the “average diameter” in the “Analysis / volumetric statistical value (arithmetic average)” window is the weight-averaged particle diameter (D4). EXAMPLES

[0139] The present invention is described in more detail by the following manufacturing examples and other examples, but these do not limit the present invention. Unless otherwise indicated, parts and percentages in the following mixtures are on a mass basis. <Amorpher Polyester-Herstellungsbeispiel (1)> • Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane: 71.1 parts (0.20 mol, 100.0 mol-% relative to the total mol number of the alcohol component) • Terephthalic acid: 29.9 parts (0.18 mol, 100.0 mol% relative to the total mole number of the carboxylic acid component) • Titanium dihydroxybis(triethanolaminate): 0.72 parts per 100 parts of the total amount of the monomer component

[0140] These materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. The interior of the flask was filled with nitrogen gas, followed by a stepwise increase in temperature while stirring. The reaction was carried out for 5 hours at 200°C with stirring to obtain an amorphous polyester (1).

[0141] The obtained amorphous polyester (1) had a weight-averaged molecular weight by GPC of 5700. It had a softening point of 105°C, a glass transition temperature of 56°C, and an acidity of 6 mg KOH / g. <Amorpher Polyester-Herstellungsbeispiele (2) bis (15) und (17) bis (31)>

[0142] Amorphous polyester resins (2) to (15) and (17) to (31) were obtained by carrying out the reaction exactly as in the amorphous polyester preparation example (1), but by changing the alcohol component or carboxylic acid component used, the molar ratio, and the catalyst, as shown in Table 1, and by controlling the reaction time and temperature to obtain the properties specified in Table 1, e.g., Mw. The mass parts of the starting materials were adjusted to provide the same total molar number for the alcohol component and carboxylic acid component as in preparation example (1). The properties of the obtained amorphous polyesters are given in Table 1. <Amorpher Polyester-Herstellungsbeispiel (16)>

[0143] 300 parts of ethyl acetate were introduced into a 5 L separable flask, and 100 parts of the amorphous polyester (1) were added stepwise and dissolved under stirring with a three-in-one motor (Shinto Scientific Co., Ltd.). Then, 0.72 parts of tin di(2-ethylhexanoate) were added and stirred, and an amorphous polyester (16) was subsequently obtained by removing the solvent under reduced pressure. The properties of the obtained amorphous polyester (16) are given in Table 1. <Amorpher Polyester-Herstellungsbeispiel (32)>

[0144] 300 parts of ethyl acetate were introduced into a 5 L separable flask, and 100 parts of the amorphous polyester (17) were added stepwise and dissolved under stirring with a three-in-one motor (Shinto Scientific Co., Ltd.). Then, 1.00 part of titanium dihydroxybis(triethanolaminate) was added and stirred, and an amorphous polyester (32) was subsequently obtained by removing the solvent under reduced pressure. The properties of the obtained amorphous polyester (32) are given in Table 1. [Table 1] alcohol acid Tin compound or titanium compound (number of parts per 100 parts of the monomer compound) Mw Softening point Tm (°C) Tg(°C) Acidity value mgKOH / g amorphous polyester No. BPA-PO(2.2) PG Terephthalic acid Adipic acid tin dioctanoate Tin di(2-ethylhexanoate) Dibutyltin oxide Titanium tetrabutoxide Titanium terephthalate Titanium dihydroxybis(triethanolaminate) (1) 100 mol% 0 mol% 100 mol% - - - - - 0,72 5700 105 56 7 (2) 100 mol% 0 mol% 100 mol% - - - - 1,20 - - 6000 100 55 5 (3) 100 mol% 0 mol% 100 mol% - - - - - 1,00 - 5200 102 55 5 (4) 100 mol% 0 mol% 100 mol% - - - - - - 1,60 5500 100 56 7 (5) 100 mol% 0 mol% 100 mol% - - - - - - 0,50 6000 98 56 7 (6) 100 mol% 0 mol% 100 mol% - - - - - - 0,16 5200 104 56 6 (7) 100 mol% 0 mol% 100 mol% - - - - - - 1,80 4600 99 56 9 (8) 100 mol% 0 mol% 100 mol% - - - - - - 1,00 4000 100 56 10 (9) 100 mol% 0 mol% 100 mol% - - - - - - 1,40 6700 108 56 6 (10) 95 mol% 5 mol% 100 mol% - - - - - - 0,72 5600 105 56 7 (11) 85 mol% 15 mol% 100 mol% - - - - - - 0,68 5400 105 56 10 (12) 50 mol% 50 mol% 100 mol% - - - - - - 0,64 5200 104 54 16 (13) 0 mol% 100 mol% 100 mol% - - - - - - 0,60 5000 102 53 24 (14) 100 mol% 0 mol% 100 mol% - - - - - - 0,16 6000 106 56 7 (15) 100 mol% 0 mol% 100 mol% - - - - - - 1,40 8000 110 58 5 (16) 100 mol% 0 mol% 100 mol% - - 0,72 - - - 0,72 5700 105 54 6 (17) 100 mol% 0 mol% 95 mol% 5 mol% - 0,50 - - - - 5300 110 54 6 (18) 100 mol% 0 mol% 95 mol% 5 mol% - - 0,40 - - - 6200 107 55 8 (19) 100 mol% 0 mol% 95 mol% 5 mol% 0,28 - - - - - 6000 112 54 6 (20) 100 mol% 0 mol% 95 mol% 5 mol% 0,85 - - - - - 5200 109 54 6 [Table 1] continued alcohol acid Tin compound or titanium compound (number of parts per 100 parts of the monomer compound) Mw Softening point Tm (°C) Tg(°C) Acidity value mgKOH / g amorphous polyester No. BPA-PO(2.2) PG Terephthalic acid Adipic acid tin dioctanoate Tin di(2-ethylhexanoate) Dibutyltin oxide Titanium tetrabutoxide Titanium terephthalate Titanium dihydroxybis(triethanolaminate) (21) 100 mol% 0 mol% 95 mol% 5 mol% - 0,12 - - - - 5500 107 54 6 (22) 100 mol% 0 mol% 95 mol% 5 mol% - 1,20 - - - - 4700 112 54 9 (23) 100 mol% 0 mol% 95 mol% 5 mol% - 0,60 - - - - 4000 102 54 12 (24) 100 mol% 0 mol% 95 mol% 5 mol% - 0,80 - - - - 6900 112 57 5 (25) 100 mol% 0 mol% 95 mol% 5 mol% - 0,70 - - - - 8200 115 60 4 (26) 100 mol% 0 mol% 95 mol% 5 mol% 0,64 - - - - - 8200 115 60 4 (27) 95 mol% 5 mol% 95 mol% 5 mol% 0,68 - - - - - 8100 115 60 4 (28) 85 mol% 15 mol% 95 mol% 5 mol% 0,70 - - - - - 8300 115 59 4 (29) 50 mol% 50 mol% 95 mol% 5 mol% 0,65 - - - - - 8000 114 57 12 (30) 0 mol% 100 mol% 95 mol% 5 mol% 0,60 - - - - - 8500 116 57 15 (31) 100 mol% 0 mol% 95 mol% 5 mol% - 0,06 - - - - 4800 108 55 7 (32) 100 mol% 0 mol% 100 mol% - - 0,50 - - - 1,00 5300 110 54 6

[0145] The following abbreviations are used in the table. BPA-PO(2,2) Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane PG Propylene glycol <Toner-Herstellungsbeispiel 1> • amorphous polyester resin (1) 50 pieces • amorphous polyester resin (17) 50 pieces • Fischer-Tropsch wax (peak temperature of maximum endothermic peak = 89°C) parts • CI Pigment Blue 15:3 5 parts • Aluminum 3,5-di-t-butyl salicylate compound 0.5 parts

[0146] Using a Henschel mixer (model FM-75, Nippon Coke & Engineering Co., Ltd.), these materials were mixed at a rotation rate of 20 s. -1 The mixture was blended for a rotation time of 5 minutes; then kneaded at an operating temperature of 130°C using a twin-screw kneader (Model PCM-30, Ikegai Corp) set to a temperature of 120°C. The resulting kneaded material was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized material was then finely pulverized using a mechanical pulverizer (T-250, Freund-Turbo Corporation). Additionally, classification was performed using a Faculty F-300 (Hosokawa Micron Corporation) to obtain toner particles. The operating conditions were a classifier rotor rotation rate of 130 s⁻¹. -1 and a dispersion rotor rotation rate of 120 s -1 .

[0147] A toner 1 was obtained by adding to 100 parts of the obtained toner particle 1 1.0 parts of hydrophobic silica particles, which have a BET specific surface area of ​​25 m² 2 / g had and which had been subjected to a surface treatment with 4 wt% hexamethyldisilazane, and 0.8 parts hydrophobic silica fine particles, which had a BET specific surface area of ​​100 m² 2 / g and had been subjected to a surface treatment with 10 wt% polydimethylsiloxane, and mixed with a Henschel mixer (Model FM-75, Nippon Coke & Engineering Co., Ltd.) at a rotation rate of 30 s -1 for a rotation time of 10 minutes. Toner 1 had a weight-averaged particle diameter (D4) of 6.2 µm.

[0148] The Sn / Ti abundance ratio provided by X-ray fluorescence analysis for Sn and Ti present in the amorphous polyester used in toner manufacturing example 1 was 61 / 39 and the total content of Sn and Ti was 1100 ppm relative to the mass of the amorphous polyester. <Toner 2 bis 23 und 27 bis 33-Herstellungsbeispiel>

[0149] Toners 2 to 23 and 27 to 33 were obtained by a procedure similar to the preparation example for toner 1, but with modifications to the amorphous polyester used as a starting material and its numerical components, as indicated in Table 2. Table 2 gives the Sn / Ti abundance ratio and content, provided by X-ray fluorescence analysis, for Sn and Ti present in the amorphous polyesters used in the toner 2 to 23 and 27 to 33 preparation examples. (Preparation of a dispersion of amorphous polyester (1) particles)

[0150] A mixed solvent of 250 parts ethyl acetate and 50 parts isopropyl alcohol was introduced into a 5-L separable flask; 200 parts amorphous polyester (1) were added stepwise; and an oil phase was obtained by dissolving under stirring with a three-in-one motor (Shinto Scientific Co., Ltd.). Phase inversion emulsification was carried out by the dropwise addition of an appropriate amount of a dilute aqueous ammonia solution to this stirred oil phase and the additional dropwise addition of 1000 parts deionized water. Solvent removal was performed under reduced pressure using an evaporator to obtain a dispersion of amorphous polyester (1) particles.

[0151] (Preparation of a dispersion of amorphous polyester (13) particles, a dispersion of amorphous polyester (17) particles and a dispersion of amorphous polyester (30) particles)

[0152] A dispersion of amorphous polyester (13) particles, a dispersion of amorphous polyester (17) particles and a dispersion of amorphous polyester (30) particles were obtained by the procedure as in the previously mentioned preparation of a dispersion of amorphous polyester (1) particles, but changing the amorphous polyester (1) used there to amorphous polyester (13), amorphous polyester (17), and amorphous polyester (30), respectively. (Preparation of a wax dispersion) • deionized water 800 pieces • Fischer-Tropsch wax (maximum endothermic peak temperature = 200 pieces (89°C) • anionic surfactant (Neogen RK, DKS Co., Ltd.) 10 pieces

[0153] The preceding components were heated to 95°C and carefully dispersed using an IKA Ultra-Turrax T50, followed by dispersion treatment with a pressure ejection homogenizer to obtain a wax dispersion with a solids fraction of 20 wt%. (Preparation of a dye particle dispersion) • CI Pigment Blue 15:3 (100 pieces) • Sodium dodecylbenzenesulfonate (5 parts) • deionized water (400 pieces)

[0154] These were mixed and dispersed using a sand mill to obtain a dye particle dispersion. <Toner- Manufacturing example 24> • Dispersion of amorphous polyester (13) particles 700 pieces • Dispersion of amorphous polyester (30) particles 300 pieces • Dye particle dispersion 40 pieces • Wax dispersion 50 pieces • Sodium dodecylbenzenesulfonate 5 parts

[0155] The dispersion of amorphous polyester (13) particles, the dispersion of amorphous polyester (30) particles, the wax dispersion, and the sodium dodecylbenzenesulfonate were mixed uniformly in a reactor (1-liter flask with partition, anchor impeller). Separately, the dye particle dispersion was mixed to uniformity in a 500 mL beaker and added stepwise to the reactor with stirring to obtain a mixed dispersion. While stirring the resulting mixed dispersion, 0.5 parts of an aqueous aluminum sulfate solution were added dropwise as solids to induce the formation of aggregate particles.

[0156] After completion of the dropwise addition, the interior of the system was substituted using nitrogen and held for 1 hour at 50°C and for 1 hour at 55°C.

[0157] The temperature was then increased and held at 90°C for 30 minutes. The temperature was subsequently reduced to 63°C, followed by a holding period of 3 hours to induce the formation of fused particles. The reaction was carried out under a nitrogen atmosphere. After the specified time period, cooling to room temperature was performed at a rate of 0.5°C per minute.

[0158] After cooling, the solid-liquid reaction product was subjected to a solid-liquid separation at a pressure of 0.4 MPa on a 10 L pressurized filter to obtain a toner cake. Deionized water was then added to the pressurized filter to its full level, and washing was performed at a pressure of 0.4 MPa. This washing process was repeated three times. The toner cake was then dispersed in 1 L of a 50:50 methanol / water solution containing 0.15 parts of a nonionic surfactant to obtain a dispersion of surface-treated toner particles.

[0159] This toner particle dispersion was poured into a press filter and 5 L of deionized water were added. Solid-liquid separation was then carried out at a pressure of 0.4 MPa, followed by fluidized bed drying at 45°C to obtain toner particle size 24.

[0160] A toner 24 was obtained by adding, to 100 parts of the obtained toner particle 24, 1.0 part of hydrophobic silica particles, which have a BET specific surface area of ​​25 m² 2 / g and which had undergone surface treatment with 4 wt% hexamethyldisilazane and 0.8 parts hydrophobic silica fine particles, which had a BET specific surface area of ​​100 m² 2 / g and which had been subjected to a surface treatment with 10 parts by mass of polydimethylsiloxane, and mixed with a Henschel mixer (model FM-75, Nippon Coke & Engineering Co., Ltd.) at a rotation rate of 30 s -1 for a rotation time of 10 minutes. Toner 24 had a weight-averaged particle diameter (D4) of 6.2 µm. The Sn / Ti abundance ratio, provided by X-ray fluorescence analysis, for Sn and Ti present in the amorphous polyester used in Toner Production Example 24 was 51 / 49, and the total content of Sn and Ti was 1000 ppm relative to the mass of the amorphous polyester. <Toner-Herstellungsbeispiel 25>

[0161] Toner 25 was obtained by a procedure as in Toner Production Example 24, but changing the amorphous polyester (13) dispersion to the amorphous polyester (1) particle dispersion and changing the amorphous polyester (30) particle dispersion to the amorphous polyester (26) particle dispersion. Toner 25 had a weight-averaged particle diameter (D4) of 6.2 µm. The Sn / Ti abundance ratio, provided by X-ray fluorescence analysis, for Sn and Ti present in the amorphous polyester used in Toner Production Example 25 was 46 / 54, and the total amount of Sn and Ti was 1100 ppm relative to the mass of the amorphous polyester. <Toner-Herstellungsbeispiel 26>

[0162] Toner 26 was obtained by the procedure described in Toner Preparation Example 24, except that the amorphous polyester (13) particle dispersion was changed to 500 parts of the amorphous polyester (1) particle dispersion and the amorphous polyester (30) particle dispersion was changed to 500 parts of the amorphous polyester (17) particle dispersion. Toner 26 had a weight-averaged particle diameter (D4) of 6.2 µm. The Sn / Ti abundance ratio, provided by X-ray fluorescence analysis, for Sn and Ti present in the amorphous polyester obtained in Toner Preparation Example 26 was 61 / 39. [Table 2] Toner No. amorphous polyester (per 100 pieces) Sn / Ti mamorphic polyester Total abundance of tin and titanium (ppm) Manufacturing process Resin 1 used amorphous polyester No. parts Resin 2 used eamorphous polyester No. parts Resin 3 used amorphous polyester No. parts 1 (1) 50 (17) 50 61 / 39 1100 Pulverization 2 (32) 50 (17) 50 70 / 30 2000 Pulverization 3 (1) 50 (16) 50 54 / 46 1900 Pulverization 4 (1) 20 (17) 40 (2 6) 40 38 / 62 1400 Pulverization 5 (2) 50 (17) 50 47 / 53 1500 Pulverization 6 (3) 50 (17) 50 39 / 61 1800 Pulverization 7 (1) 40 (18) 60 68 / 32 1400 Pulverization 8 (1) 28 (17) 72 74 / 26 1200 Pulverization 9 (1) 83 (17) 17 28 / 72 1000 Pulverization 10 (4) 52 (19) 48 25 / 75 1400 Pulverization 11 (5) 52 (20) 48 77 / 23 1400 Pulverization 12 (6) 50 (21) 50 60 / 40 200 Pulverization 13 (7) 50 (22) 50 61 / 39 2800 Pulverization 14 (8) 50 (23) 50 59 / 41 1400 Pulverization 15 (9) 50 (24) 50 58 / 42 2000 Pulverization 16 (9) 50 (25) 50 54 / 46 1800 Pulverization 17 (1) 50 (26) 50 67 / 33 1300 Pulverization 18 (1) 70 (26) 30 46 / 54 1100 Pulverization 19 (17) 50 (15) 50 45 / 55 1500 Pulverization 20 (10) 70 (27) 30 48 / 52 1200 Pulverization 21 (11) 70 (28) 30 52 / 48 1100 Pulverization 22 (12) 70 (29) 30 50 / 50 1100 Pulverization 23 (13) 70 (30) 30 51 / 49 1000 Pulverization 24 (13) 70 (30) 30 51 / 49 1000 Aggregation 25 (1) 70 (26) 30 46 / 54 1100 Aggregation 26 (1) 50 (17) 50 61 / 39 1100 Aggregation 27 (17) 50 (21) 50 100 / 0 800 Pulverization 28 (1) 50 (4) 50 0 / 100 1400 Pulverization 29 (1) 20 (17) 80 86 / 14 1300 Pulverization 30 (1) 88 (17) 12 15 / 85 900 Pulverization 31 (1) 50 (31) 50 10 / 90 500 Pulverization 32 (14) 50 (17) 50 88 / 12 800 Pulverization 33 (15) 50 (25) 50 54 / 46 1800 Pulverization <Magnetisches Nuclear particle 1 - Production example> • Step 1 (Weighing - Mixing step): Fe2O3 62.7 pieces MnCO3 29.5 pieces Mg(OH)2 6.8 pieces SrCO3 1.0 parts

[0163] The ferrite starting materials were weighed out so that these materials assumed the composition ratio specified below. However, pulverization and mixing for 5 hours followed using a dry vibratory mill with a 1 / 8 inch diameter stainless steel ball. • Step 2 (Pre-burning step):

[0164] The resulting powder was converted into an approximately 1 mm square pellet using a roller compactor. After removing the coarse powder using a vibrating screen with a 3 mm opening and subsequently removing the fines using a vibrating screen with a 0.5 mm opening, the pellets were fired for 4 hours at a temperature of 1000°C in a kiln-type furnace under a nitrogen atmosphere (oxygen concentration: 0.01% by volume) to produce pre-fired ferrite. The composition of the resulting pre-fired ferrite was as follows. (MnO) a (MgO) b (SrO) c (Fe2O3) d

[0165] In this formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393 • Step 3 (Powdering step):

[0166] The resulting pre-burned ferrite was pulverized to approximately 0.3 mm using a crusher, followed by pulverization for 1 hour in a wet ball mill using 1 / 8-inch diameter zirconium dioxide balls and the addition of 30 parts water per 100 parts of pre-burned ferrite. The resulting slurry was then milled for 4 hours in a wet ball mill using 1 / 16-inch diameter aluminum oxide balls to obtain a ferrite slurry (finely powdered pre-burned ferrite). • Step 4 (Granulation step):

[0167] One part of ammonium polycarboxylate as a dispersant and two parts of polyvinyl alcohol as a binder per 100 parts of pre-burned ferrite were added to the ferrite slurry, followed by granulation into spherical particles using a spray dryer (manufacturer: Okawara Kakohiki Co., Ltd.). The particle size was adjusted to the resulting particles, which were then heated for two hours at 650°C using a rotary kiln to remove the dispersant and organic binder components. • Step 5 (firing step):

[0168] To control the firing atmosphere, the temperature was increased from room temperature to 1300°C over 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration: 1.00% by volume); firing was then carried out for 4 hours at a temperature of 1150°C. This was followed by cooling to a temperature of 60°C over 4 hours; a return from the nitrogen atmosphere to ambient air; and removal at a temperature at or below 40°C. • Step 6 (Classification step):

[0169] After the aggregated particles were crushed, the strongly magnetic fraction was removed by magnetic separation and the coarse particles were removed by sieving on a sieve with an opening of 250 µm to obtain a magnetic core particle 1 with a 50% particle diameter on a volume basis (D50) of 37.00 µm. <Anfertigung von Beschichtungsharz 1> Cyclohexyl methacrylate monomer 26.8% by mass Methyl methacrylate monomer 0.2 mass % Methyl methacrylate macromonomer 8.4% by mass (Macromonomer with a weight-averaged methacryloyl group at one end) Molecular weight of 5000 and toluene 31.3% by mass Methyl ethyl ketone 31.3% by mass Azobisisobutyronitrile 2.0 mass %

[0170] Cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were introduced into a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a stirrer. Nitrogen gas was introduced to carefully convert to a nitrogen atmosphere. The mixture was heated to 80°C, and azobisisobutyronitrile was added. Polymerization was carried out under reflux for 5 hours. The copolymer was precipitated by pouring hexane into the resulting reaction product, and the precipitate was separated by filtration and then vacuum-dried to obtain a coating resin 1. Thirty parts of the coating resin 1 were subsequently dissolved in 40 parts toluene and 30 parts methyl ethyl ketone to obtain a polymer solution 1 (30 wt% solid fraction). <Anfertigung von Beschichtungsharzlösung 1> Polymer solution 1 (30% resin solids concentration) 33.3% by mass toluene 66.4% by mass Carbon Black (Regal 330, Cabot Corporation) 0.3 mass % (Primary particle diameter = 25 nm, specific surface area due to nitrogen adsorption = 94 m²) 2 / g, DBP absorption = 75 mL / 100g) were dispersed for 1 hour using a paint shaker and zirconium dioxide spheres with a diameter of 0.5 mm. The resulting dispersion was filtered through a 0.5 µm membrane filter to obtain a coating resin solution 1. <Magnetischer Träger 1-Herstellungsbeispiel> (Resin coating step):

[0171] The coating resin solution 1 was introduced into a vacuum-degassed kneader, which was maintained at room temperature, to provide 2.5 parts of the resin component relative to the magnetic core particle 1 (100 parts by mass). After introduction, stirring was performed for 15 minutes at a rotation rate of 30 rpm, and after at least a certain amount (80 wt%) of the solvent had evaporated, the temperature was increased to 80°C while stirring under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling. The resulting magnetic carrier, after fractionation and separation of the weakly magnetic product by magnetic selection and passage through a 70 µm aperture sieve, was classified using an air classifier to obtain a magnetic carrier 1 with a 50% particle diameter on a volume basis (D50) of 38.2 µm. <Zwei-Komponenten-Entwickler-Herstellungsbeispiel 1>

[0172] Toner 1 (8.0 parts) was added to the magnetic carrier 1 (92.0 parts) and mixing was carried out using a V-mixer (V-20, Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1. <Two-Component Developer Manufacturing Examples 2 to 33>

[0173] Two-component developers 2 to 33 were obtained by performing the production as in the two-component developer manufacturing example 1, but changing the toner as shown in Table 3. [Table 3] Two-component developer toner carrier Two-component developer 1 Toner 1 magnetic carrier 1 Two-component developer 2 Toner 2 magnetic carrier 1 Two-component developer 3 Toner 3 magnetic carrier 1 Two-component developer 4 Toner 4 magnetic carrier 1 Two-component developer 5 Toner 5 magnetic carrier 1 Two-component developer 6 Toner 6 magnetic carrier 1 Two-component developer 7 Toner 7 magnetic carrier 1 Two-component developer 8 Toner 8 magnetic carrier 1 Two-component developer 9 Toner 9 magnetic carrier 1 Two-component developer 10 Toner 10 magnetic carrier 1 Two-component developer 11 Toner 11 magnetic carrier 1 Two-component developer 12 Toner 12 magnetic carrier 1 Two-component developer 13 Toner 13 magnetic carrier 1 Two-component developer 14 Toner 14 magnetic carrier 1 Two-component developer 15 Toner 15 magnetic carrier 1 Two-component developer 16 Toner 16 magnetic carrier 1 Two-component developer 17 Toner 17 magnetic carrier 1 Two-component developers 18 Toner 18 magnetic carrier 1 Two-component developers 19 Toner 19 magnetic carrier 1 Two-component developers 20 Toner 20 magnetic carrier 1 Two-component developer 21 Toner 21 magnetic carrier 1 Two-component developer 22 Toner 22 magnetic carrier 1 Two-component developers 23 Toner 23 magnetic carrier 1 Two-component developers 24 Toner 24 magnetic carrier 1 Two-component developers 25 Toner 25 magnetic carrier 1 Two-component developers 26 Toner 26 magnetic carrier 1 Two-component developers 27 Toner 27 magnetic carrier 1 Two-component developers 28 Toner 28 magnetic carrier 1 Two-component developer 29 Toner 29 magnetic carrier 1 Two-component developers 30 Toner 30 magnetic carrier 1 Two-component developer 31 Toner 31 magnetic carrier 1 Two-component developer 32 Toner 32 magnetic carrier 1 Two-component developer 33 Toner 33 magnetic carrier 1 [1. Evaluation of the hot offset resistor]

[0174] A Canon Inc. imageRUNNER ADVANCE C9075PRO full-color copier was modified to allow free adjustment of the fusing temperature and processing speed, and a test of the fusing temperature range was performed using two-component developer 1. Regarding the image, unfixed images were produced in a single-color mode under normal temperature and humidity conditions (temperature = 23°C, relative humidity = 50% to 60%) with a toner coating level on the paper of 1.2 mg / cm². 2 manufactured. GF-C081 Copy paper (A4, basis weight = 81.4 g / m²) 2 , sold by Canon Marketing Japan Inc.) was used as the evaluation paper and an image was produced that had an image print percentage of 25%.

[0175] The generated images were then fixed in a normal temperature, low humidity environment (temperature = 23°C, relative humidity no more than 5%) at a processing speed set to 450 mm / second and with the fixing temperature increased in 5°C increments, starting at 120°C. The upper limit temperature at which no offset was generated was taken as the hot offset resistance temperature.

[0176] The hot offset resistance temperature was evaluated using the following criteria. The results of the evaluation are given in Table 4.

[0177] (Evaluation criteria for the hot offset resistance temperature) A: at least 210°C (extremely good) B: at least 200°C and less than 210°C (good) C:Invention (at least 190°C and less than 200°C are maintained) (the effects of the present D: less than 190°C [2. Evaluation of fixer circulation resistance]

[0178] Using the evaluation machine that was used in the previously mentioned evaluation of the hot offset resistor, an unfixed image (toner deposition level = 1.2 mg / cm²) was obtained. 2 A 60 mm long groove was created in the direction of paper feed, starting 1 mm from the inlet edge of the evaluation paper. Using the same settings, 10 sheets of the evaluation sample, bearing the unfixed image, were produced. CS-680 (A4, basis weight = 68.0 g / m²) 2 , sold by Canon Marketing Japan Inc.) was used as the evaluation paper.

[0179] Then, in a high-temperature, high-humidity environment (temperature = 30°C, relative humidity = 80%), 10 sheets were continuously processed at a paper transport speed of 450 mm / second with a fusing temperature that was increased in 5°C increments of 150°C. The upper temperature at which no paper recirculation occurred during fusing was considered the fusing recirculation resistance temperature. The evaluation results were assessed according to the following criteria. The evaluation results are presented in Table 4. A: at least 200°C (very good) B: at least 185°C and less than 200°C (good) C:Invention (at least 170°C and less than 185°C will be maintained) (the effects of the present D: less than 170°C [3. Evaluation of low-temperature fixability]

[0180] A low-temperature fixability test was performed using the two-component developer 1 and the evaluation machine used in the previously mentioned hot-offset resistance evaluation. Regarding the image, unfixed images were printed in a single-color mode under normal temperature and humidity conditions (temperature = 23°C, relative humidity = 50% to 60%) with a toner deposition level on the paper set to 1.2 mg / cm². 2 manufactured. GF-C081 Copy paper (A4, basis weight = 81.4 g / m²) 2 , sold by Canon Marketing Japan Inc.) was used as the evaluation paper and an image was produced that had an image print percentage of 25%.

[0181] Then, during operation in a low-temperature, low-humidity environment (temperature = 15°C, relative humidity no more than 10%) with a process speed set to 450 mm / second and an increase in the fixing temperature in 5°C steps in sequence of 120°C, the low-temperature fixing temperature was taken as the lower limit temperature at which no offset was generated. (Criteria for evaluating the low-temperature fixing temperature) A: less than 150°C (very good) B: at least 150°C and less than 160°C (good) C:Invention (at least 160°C and less than 170°C were obtained) (the effects of the present D: at least 170°C [4. Evaluation of charging stability]

[0182] The evaluation described below was performed using a Canon Inc. ImagePress C800 full-color copier as the image-forming apparatus, with the aforementioned two-component developer added to the cyan developing unit of the image-forming apparatus. A modification was made by removing the mechanism that ejects the excess magnetic carrier from the developing unit.

[0183] Settings were adjusted so that the toner application level on the paper for the FFh image (fixed image) is 0.45 mg / cm². 2 FFh refers to values ​​that express 256 gradations in a hexadecimal format, where 00h is the first gradation (white background) of the 256 gradations and FF is the 256th gradation (solid region) of the 256 gradations.

[0184] A continuous 10,000-sheet print output test was performed at a frame rate of 25% in a normal temperature, normal humidity (NN) environment (temperature = 23°C, relative humidity of at least 50% and not more than 60%). During the 10,000-sheet continuous feed, the paper was fed using the same development conditions as for the first sheet (no calibration). GF-10081 standard copy paper (A4, basis weight = 81.4 g / m²) was used. 2 , sold by Canon Marketing Japan Inc.) was used for the evaluation paper in the 10000 image print output endurance test.

[0185] The evaluation criteria and the evaluated items on the ejected image, both initially (first print) and after a 10,000th sheet continuous paper feed, are listed below.

[0186] The results of the evaluation are given in Table 4. (Measurement of image density)

[0187] Using an X-Rite color reflectance densiometer (500 series, X-Rite, Inc.), the image density of the FFh image area: fixed area was measured both initially (first print) and at the 10,000th print. The evaluation was based on the difference Δ between the two image densities using the following criteria. The results of the evaluation are given in Table 4. A: less than 0.05 (very good) B: at least 0.05 and less than 0.10 (good) C:Invention at least 0.10 and less than 0.15 (these will be received) Effects of the present D: at least 0.15 <Beispiele 2 bis 15, Referenzbeispiele 16 bis 26 und Vergleichsbeispiele 1 bis 7>

[0188] Evaluations were performed using a procedure similar to Example 1, but changing the two-component developer used in the evaluations to the two-component developers shown in Table 3. The results of the evaluations are given in Table 4. [Table 4] Example No. Two-component developer no. Hot offset resistor Evaluation Fixing circulation resistance Evaluation Low-temperature fixability Evaluation Density difference after NND long-term test (%) Evaluation 1 1 225 A 210 A 150 B 0,03 A 2 2 210 A 195 B 150 B 0,03 A 3 3 210 A 195 B 150 B 0,04 A 4 4 215 A 205 A 150 B 0,04 A 5 5 220 A 205 A 150 B 0,04 A 6 6 220 A 205 A 150 B 0,04 A 7 7 200 B 185 B 150 B 0,04 A 8 8 195 C 175 C 150 B 0,07 B 9 9 195 C 175 C 150 B 0,06 B 10 10 195 C 175 C 150 B 0,07 B 11 11 195 C 175 C 150 B 0,07 B 12 12 200 B 185 B 150 B 0,06 B 13 13 225 A 205 A 145 A 0,09 B 14 14 220 A 205 A 145 A 0,07 B 15 15 205 B 185 B 155 B 0,04 A Ref. 16 16 195 C 170 C 160 C 0,03 A Ref. 17 17 200 B 200 A 155 B 0,03 A Ref. 18 18 205 B 205 A 155 B 0,03 A Ref. 19 19 200 B 200 A 155 B 0,03 A Ref. 20 20 205 B 200 A 155 B 0,04 A Ref. 21 21 205 B 190 B 155 B 0,04 A Ref. 22 22 200 B 185 B 155 B 0,07 B Ref. 23 23 200 B 185 B 155 B 0,09 B Ref. 24 24 195 C 175 C 155 B 0,12 C Ref. 25 25 205 B 180 C 155 B 0,10 C Ref. 26 26 210 A 195 B 150 B 0,09 B Comparison 1 27 180 D 165 D 155 B 0,12 C Comparison 2 28 180 D 165 D 155 B 0,13 C Comparison 3 29 180 D 165 D 155 B 0,12 C Comparison 4 30 180 D 165 D 155 B 0,12 C Comparison 5 31 180 D 165 D 155 B 0,10 C Comparison 6 32 180 D 165 D 155 B 0,10 C Comparison 7 33 185 D 165 D 170 D 0,06 B

[0189] While the present invention has been described with reference to exemplary embodiments, it is understood that the invention is not limited to these disclosed exemplary embodiments. The scope of protection of the following claims is to be given the broadest possible interpretation to encompass all such modifications and equivalent structures and functions.< / herstellungsverfahren>