TONER

Abstract

A toner contains toner particles that include a binder resin and a release agent W. The toner has a glass transition temperature Tg of 70 °C or lower. The binder resin contains an amorphous resin A, which is a polyester with a polyester backbone formed from: (i) a polyethylene terephthalate structural segment; and (ii) at least one unit with a specific structure. The release agent W is an ester wax. The SP value SP A of the amorphous resin A, the SP value SP W of the release agent W, W EG the ethylene glycol-derived structures in the amorphous resin A and W CH the specific structures of (ii) in the amorphous resin A fulfill specific relationships.

Description

BACKGROUND OF THE INVENTION Area of ​​the invention

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

[0002] The recent expansion of electrophotographic processes into the print-on-demand (POD) sector has created a need for toners capable of handling high-speed printing. Additionally, reducing the environmental impact of the materials used must be considered.

[0003] From the point of view of increasing printing speed, polyester, which uses a bisphenol-A alkylene oxide adduct as a raw material monomer, is used as a binder resin in a toner (see disclosed Japanese patent no. 2000-172008).

[0004] The reuse of plastic products, such as used PET bottles, has become a major drawback, as have the environmental and resource disadvantages. With the increasing number of PET bottles sold, there is a growing demand for higher recycling rates. Methods of recycling PET bottles include their use in food trays and other film applications, in clothing and other textile applications, and in bottle-to-bottle recycling, which is a form of horizontal recycling.

[0005] Accordingly, it has been proposed that used PET bottles (so-called recycled PET bottles) made from polyester recovered from waste be used in the field of electrophotography (see disclosed Japanese patent nos. 8-239409 and 2024-27954).

[0006] The present inventors investigated toners incorporating a polyethylene terephthalate structure into an amorphous polyester using a bisphenol A alkylene oxide adduct, with reference to disclosed Japanese patents nos. 2000-172008, 8-239409, and 2024-27954. However, the inventors found that in high-speed devices compatible with the 3D printing (POD) range, the accumulation of the release agent on the cleaning blade, which is used to scrape and collect the toner remaining on the photosensitive unit after transfer, can cause defective images. The toner reaching the cleaning section adheres to the cleaning blade and heats up due to friction with the photosensitive unit.In the case of high-speed devices compatible with the POD range, the amount of heat generated is large, and consequently the release agent seeps out as the toner heats up (the so-called bleed-out phenomenon).

[0007] The release agent that seeps out runs through the contact area between the cleaning blade and the photosensitive unit, adhering to and accumulating on the back of the cleaning blade. Then, after images have formed on many sheets of paper, the accumulated release agent pushes the cleaning blade upwards, creating a gap through which toner flows. By this time, the toner has already been heated to some extent, so the pressure from the cleaning blade as the toner flows through causes the toner to melt and adhere to the surface of the photosensitive unit, resulting in defective images.

[0008] Amorphous polyester incorporating a polyethylene terephthalate (PET) structure, which exhibits high polarity, is less miscible with the release agent. Consequently, amorphous polyester incorporating a polyethylene terephthalate structure has a lower affinity for the release agent than that utilizing only bisphenol A alkylene oxide adducts, thus promoting leaching of the release agent. This is advantageous with respect to hot-offset resistance but does not sufficiently reduce the aforementioned leaching phenomenon of the release agent.

[0009] The affinity of the amorphous polyester for the release agent can be improved by reducing the amount of polyethylene terephthalate structure incorporated into the amorphous polyester. However, this reduces the effect of improving hot-offset resistance, which is achieved by promoting the seepage of the release agent.

[0010] Therefore, when a toner containing a polyethylene terephthalate structure is used in a high-speed device, the challenge is to achieve both excellent hot-offset resistance, obtained through sufficient seepage of the release agent during fixing, and the reduction of defective images caused by the accumulation of the release agent in the cleaning section. SUMMARY

[0011] The present disclosure provides a toner that achieves both excellent hot-offset resistance and the reduction of defective images caused by the accumulation of the separating agent in the cleaning section, even in high-speed devices compatible with the POD market.

[0012] The present disclosure relates to a toner having a glass transition temperature Tg of 70 °C or lower, comprising: Toner particles containing a binder resin and a release agent W, wherein the binder resin, which contains an amorphous resin A, is a polyester with a polyester backbone formed from: (i) a polyethylene terephthalate structural segment; and (ii) at least one structure selected from the group consisting of a unit represented by formula (1), a unit represented by formula (2), a unit represented by formula (3) and a unit represented by formula (4): where in formula (1), R1 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, A1 represents a hydrocarbon group, * represents a bonding site of the polyester skeleton, and m represents an integer of 2 or more, where in formula (2), R2 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, B1 represents a hydrocarbon group, * represents a bonding site of the polyester skeleton, and n represents an integer of 2 or more, where in formula (3), Each * represents a bonding point of the polyester skeleton, and x represents an integer from 6 to 16, where in formula (4), Each * represents a bonding site of the polyester skeleton, and y represents an integer from 6 to 16, the release agent W is an ester wax that satisfies the following relationship (C) with the amorphous resin A: 1.90≤SPA−SPW≤2.85 where SP A (cal / cm 3 ) 0,5 denotes the SP value of the amorphous resin A and SP W (cal / cm 3 ) 0,5 denotes the SP value of the release agent W, The amorphous resin A satisfies the following relationship (H): 0.27≤WCH / WEG≤1.06 where W EG (mol-%) denotes the percentage of the number of moles of structures in the amorphous resin A that are derived from ethylene glycol in the polyethylene terephthalate structural portion, relative to the total number of moles of alcohol-derived and carboxylic acid-derived structures that form the polyester backbone, and W CH (mol-%) denotes the percentage of the total number of moles in the amorphous resin A of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), relative to the total number of moles of the alcohol-derived structures and carboxylic acid-derived structures that form the polyester skeleton.

[0013] Further features of the present invention will become apparent from the following description of exemplary embodiments. DESCRIPTION OF THE EXECUTION FORMS

[0014] The present disclosure is described in detail below. This disclosure is not limited to the following descriptions. In the description provided herein, expressions representing numerical ranges, such as "XX or more and YY or less" and "XX to YY", refer to ranges that include the lower and upper limits, which are the endpoints unless otherwise specified. Where some numerical ranges are expressed in steps, the lower and upper limits of the respective ranges may be combined arbitrarily. A monomer unit refers to a reacted form of a monomer substance in a polymer. Crystalline polyester is a type of polyester that exhibits a distinct endothermic peak upon differential scanning calorimetry (DSC).

[0015] The present inventors have investigated a toner that achieves both sufficient hot offset resistance and the reduction of defective images caused by the accumulation of the separating agent in the cleaning section, even in high-speed devices compatible with the POD market.

[0016] The present inventors first analyzed the phenomenon of defective image generation caused by the accumulation of the release agent on the cleaning blade in a high-speed device. The toner that reaches and adheres to the cleaning blade heats up due to friction with the photosensitive element, as described above. The present inventors identified that the adhered toner in the high-speed device heated up to approximately 70 °C, a temperature range exceeding the glass transition temperature (Tg) of typical toners, which is between 55 °C and 60 °C. It is likely that the molecules of the components in the toner can migrate slowly at temperatures exceeding Tg.Toners containing a polyethylene terephthalate structure tend to cause the release agent bleeding phenomenon because the polyethylene terephthalate structure has a low affinity for the release agent.

[0017] The release agent that has seeped out of the stuck toner runs through the contact area between the cleaning blade and the photosensitive element, adhering to and accumulating on the back of the cleaning blade. If images have been formed on many sheets of paper, the accumulated release agent pushes the cleaning blade upwards, creating a gap through which toner flows. As the toner passes through this gap, it is subjected to pressure from the cleaning blade, causing it to melt and adhere to the surface of the photosensitive element. This is likely the cause of defective images.

[0018] The inventors also conducted a study to achieve both a reduction in the bleed-out phenomenon of the release agent in the cleaning section and sufficient hot-offset resistance during fixing. Specifically, the inventors investigated various combinations of binder resins and release agents that could reduce the bleed-out phenomenon of the release agent at approximately 70 °C, a temperature exceeding the Tg of toners, and allow the release agent to leach out during fixing. As a result, a toner with the following composition was identified to achieve the two aforementioned objectives.

[0019] The toner revealed herein is as follows. Toner having a glass transition temperature Tg of 70 °C or lower, the toner includes: Toner particles containing a binder resin and a release agent W, wherein the binder resin contains an amorphous resin A, which is a polyester with a polyester backbone formed from: (i) a polyethylene terephthalate structural segment; and (ii) at least one structure selected from the group consisting of a unit represented by formula (1), a unit represented by formula (2), a unit represented by formula (3) and a unit represented by formula (4): where in formula (1), R1 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, A1 represents a hydrocarbon group, * represents a bonding site of the polyester skeleton, and m represents an integer of 2 or more, where in formula (2), R2 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, B1 represents a hydrocarbon group, * represents a bonding site of the polyester skeleton, and n represents an integer of 2 or more, where in formula (3), Each * represents a bonding point of the polyester skeleton, and x represents an integer from 6 to 16, where in formula (4), Each * represents a bonding site of the polyester skeleton, and y represents an integer from 6 to 16, the release agent W is an ester wax that satisfies the following relationship (C) with the amorphous resin A: 1.90≤SPA−SPW≤2.85 where SP A (cal / cm 3 ) 0,5 denotes the SP value of the amorphous resin A and SP W (cal / cm 3 ) 0,5 denotes the SP value of the release agent W, The amorphous resin A satisfies the following relationship (H): 0.27≤WCH / WEG≤1.06 where W EG(mol-%) denotes the percentage of the number of moles of structures in the amorphous resin A that are derived from ethylene glycol in the polyethylene terephthalate structural portion, relative to the total number of moles of alcohol-derived and carboxylic acid-derived structures that form the polyester backbone, and W CH(mol-%) denotes the percentage of the total number of moles in the amorphous resin A of the units represented by formula (1), the units represented by formula (2), the units represented by formula (3), and the units represented by formula (4), relative to the total number of moles of the alcohol-derived and carboxylic acid-derived structures that form the polyester backbone. The mechanism that achieves both the reduction of defective images caused by the accumulation of the release agent in the cleaning section and sufficient hot-offset resistance, the details of which are not known, is considered as follows.

[0020] Amorphous resin A exhibits at least one structure, selected from the group consisting of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), as part of the structures forming the polyester backbone. Long-chain hydrocarbon groups, such as the alkyl and alkenyl groups contained in the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), exhibit structures similar to those of ester wax formed by an esterification reaction between a long-chain fatty acid and an aliphatic alcohol.At temperatures around 70 °C, which is the Tg of toner or higher, the long-chain hydrocarbon groups of the amorphous resin A and the long-chain hydrocarbon groups of the ester wax interact with each other through gradual molecular migration to form the ester wax, which is the release agent within the toner. The inventors believe this reduces bleed-through at the cleaning blade in high-speed devices.

[0021] Additionally, the polyester backbone of amorphous resin A features a polyethylene terephthalate structural segment and therefore exhibits a repeating structure of a condensate of terephthalic acid and ethylene glycol. The structure, derived from ethylene glycol in the polyethylene terephthalate segment, contains ester groups (-COO-) formed by esterification at close molecular distances of two carbon atoms at both ends of the ethylene glycol. Therefore, amorphous resin A contains localized ester groups. These localized ester groups form domains that enhance the percolation of the release agent.Controlling the SP values ​​of the release agent W and the amorphous resin A, which has at least one structure selected from the group consisting of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), also mediates affinity between the release agent and the amorphous resin A. The inventors believe that the presence of both low-affinity and high-affinity domains for the release agent in the amorphous resin A maintains the dispersibility of the release agent and additionally allows sufficient seepage of the release agent at approximately a fixing temperature that far exceeds the softening point of the toner, thereby providing excellent hot-offset resistance.

[0022] SP A (cal / cm 3 ) 0,5of the amorphous resin A and SPw (cal / cm²) 3 ) 0,5 The separating agent W in the present disclosure fulfills the relationship shown above (C). If the ΔSP value (SP A - SP W ), which is the difference in SP value between the amorphous resin A and the release agent W, within the range of the above relationship (C), the non-affinity between the polyethylene terephthalate structural segment, which is highly polar, and the ester wax, which is the relatively low-polarity release agent, allows the release agent to leach out sufficiently at a fixing temperature exceeding the toner's softening point, thereby improving the hot-offset resistance. If the ΔSP value (SP A - SP W ) 2.85 (cal / cm²) 3 ) 0,5If the ΔSP value (SP) is less than or greater, the amorphous resin A and the release agent W are miscible during fixation and promote the percolation of the ester wax or the release agent, thereby improving the hot offset resistance. A - SP W ) 1.90 (cal / cm²) 3 ) 0,5 or more, an excessive decrease in the viscosity of the melted toner is suppressed, which improves the release of the toner from the fuser. The ΔSP value (SP A - SP W ) is preferably 2.51 or more and 2.82 or less.

[0023] In the present revelation, the amorphous resin A fulfills the following relationship (H): 0.27≤WCH / WEG≤1.06 where W EG(mol-%) denotes the percentage of the number of moles of structures in the amorphous resin A that are derived from ethylene glycol in the polyethylene terephthalate structural portion, relative to the total number of moles of alcohol-derived and carboxylic acid-derived structures that form the polyester backbone, and W CH (mol-%) denotes the percentage of the total number of moles of the unit in the amorphous resin A represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), relative to the total number of moles of the alcohol-derived and carboxylic acid-derived structures that form the polyester backbone satisfying the following relationship (H). In the calculations of W EG and W CHThe units derived from ethylene glycol and those derived from terephthalic acid must be considered separately in the polyethylene terephthalate structural section to determine their number of moles. When calculating W EG (Molar-%) and W CH (mol-%) is the polyethylene terephthalate structural section divided into a unit derived from ethylene glycol and a unit derived from terephthalic acid to deal with the number of moles.

[0024] If W CH / W EG If the value is 0.27 or higher, the bleeding phenomenon of the release agent in high-speed devices is reduced. CH / W EG If the coefficient of friction is 1.06 or less, the release agent will advantageously seep out during fixing, thereby improving the hot offset resistance.

[0025] In the present revelation, W fulfills EG The following relationship (D) is preferred: 12.7≤WEG≤24.8

[0026] If W EG If the concentration is 12.7 mol% or higher, the proportion of ethylene glycol-derived structures in the highly polar polyethylene terephthalate in the toner increases, and the ester wax leaches out sufficiently to provide excellent hot-offset resistance. EG If the ester wax concentration is 24.8 mol% or less, it is advantageously dispersed, and bleeding at the cleaning blade can be reduced. EG is preferably 13.5 mol% or more and 24.0 mol% or less, more preferably 19.0 mol% or more and 23.5 mol% or less.

[0027] In the present revelation, W fulfills CH The following relationship (E) is preferred: 5.6≤WCH≤14.6

[0028] If W CH5.6 mol% or more improve the effect of reducing the bleed-out phenomenon of the release agent, as shown in formula (1), formula (2), formula (3), and formula (4). CH If the concentration is 14.6 mol% or less, the release agent advantageously leaches out during fixation, thereby increasing the hot offset resistance. CH is preferably 6.0 mol% or more and 14.0 mol% or less, more preferably 7.5 mol% or more and 12.5 mol% or less.

[0029] The amount of ethylene glycol-derived structures of the amorphous resin A in the toner particles, M EG , is preferably 0.32 mol / kg to 0.77 mol / kg. M EGM is the concentration of ethylene glycol-derived structures of the polyethylene terephthalate structural segment in the amorphous resin A in mol / kg, relative to the mass of the toner particles. When calculating M EG The units derived from ethylene glycol and those derived from terephthalic acid are considered separately in the polyethylene terephthalate structural section to determine their number of moles. If M EG If the concentration is 0.32 mol / kg or higher, the proportion of ethylene glycol-derived structures in the highly polar polyethylene terephthalate within the toner particles increases, and sufficient ester wax leaches out to provide excellent hot-offset resistance. When M EG If the concentration is 0.77 mol / kg or less, the ester wax is advantageously dispersed, and bleeding at the cleaning blade can be reduced. EG is preferably 0.53 mol / kg or more and 0.73 mol / kg or less.

[0030] The total amount of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4) in the amorphous resin A in the toner particles, M CH , is preferably 0.12 mol / kg to 0.48 mol / kg. M CH is the total concentration in mol / kg of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4) in the amorphous resin A, relative to the mass of the toner particles. When calculating M CH The units derived from ethylene glycol and those derived from terephthalic acid are considered separately in the polyethylene terephthalate structure section to determine their number of moles. If M CH0.12 mol / kg or more, the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4) improve the effect of reducing the leaching phenomenon of the release agent. CH If the concentration is 0.48 mol / kg or less, the release agent advantageously leaches out during fixation, thereby improving the hot offset resistance. CH is preferably 0.28 mol / kg or more and 0.38 mol / kg or less.

[0031] If the amount of the release agent W in parts by mass, relative to 100 parts by mass of the binder resin in the toner, is expressed as W W is defined, fulfill W CH and W W The following relationship (F) is preferred: 0.21≤WW / WCH≤0.69

[0032] If W W / W CHIf the concentration is 0.21 parts by mass / mol% or higher, the release agent advantageously seeps out during fixation, thereby increasing the hot offset resistance. W / W CH At 0.69 parts by mass / mol % or less, the long-chain hydrocarbon groups of the amorphous resin A, such as the alkyl and alkenyl groups, improve the effect of reducing the bleeding phenomenon of the release agent.

[0033] In the present revelation, W fulfills CH / W EG , which is the ratio of W CH to W EG is preferred the following relationship (G): 0.34≤WCH / WEG≤0.66

[0034] If W CH / W EG If the value is 0.34 or higher, the bleeding phenomenon of the release agent in high-speed devices is reduced. CH / W EGIf the coefficient of friction is 0.66 or less, the release agent leaches out advantageously during fixation, thereby improving the hot offset resistance. CH / W EG is preferably 0.41 or more and 0.66 or less, more preferably 0.50 or more and 0.61 or less.

[0035] In the present disclosure, the relationship of W W in bulk to M CH in mol / kg, W W / M CH , prefers the following relationship (I): 5.6≤WW / MCH≤26.7

[0036] If W W / M CH If the resistance is 5, 6 or more, the release agent advantageously seeps out during fixing, thereby increasing the hot offset resistance.

[0037] If W W / M CH 26.7 or less, the long-chain hydrocarbon groups of the amorphous resin A, such as alkyl and alkenyl groups, improve the effect of reducing the bleeding phenomenon of the release agent. Amorphous resin A

[0038] Amorphous resin A has a polyester skeleton formed from the following structures (i) and (ii): (i) a polyethylene terephthalate structural segment; and (ii) at least one structure selected from the group consisting of a unit represented by formula (1), a unit represented by formula (2), a unit represented by formula (3) and a unit represented by formula (4).

[0039] The polyethylene terephthalate structure used in the amorphous resin A is formed by polycondensation of ethylene glycol and terephthalic acid.

[0040] The polyester is then synthesized in an inert gas atmosphere, preferably at a temperature of about 180 °C or higher and 250 °C or lower, advantageously in the presence of an esterification catalyst and, if necessary, in the presence of an esterification promoter, polymerization inhibitor or the like.

[0041] Examples of the esterification catalyst include tin compounds, such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds, such as titanium diisopropylate bis(triethanolaminate). In some embodiments, tin compounds such as tin(II) 2-ethylhexanoate can be used.

[0042] The amount of esterification catalyst used can be 0.01 parts by mass or more, for example, 0.1 parts by mass or more, and also 1.5 parts by mass or less, for example, 1.0 parts by mass or less, relative to 100 parts by mass of the raw material monomers (alcohol component, carboxylic acid component, and PET). The esterification promoter can be, for example, gallic acid. The amount of esterification promoter used can be 0.001 parts by mass or more, for example, 0.01 parts by mass or more, and also 0.5 parts by mass or less, for example, 0.1 parts by mass or less, relative to 100 parts by mass of the raw material monomers. The polymerization inhibitor can be, for example, tert-butylcatechol. The amount of polymerization inhibitor used can be 0.001 parts by mass or more, for example 0.01 parts by mass or more, and also 0.5 parts by mass or less, for example 0.1 parts by mass or less, relative to 100 parts by mass of the raw material monomers.

[0043] In the synthesis of the polyester, polyethylene terephthalate can be added to the reaction system either at the beginning of the polycondensation reaction or during the polycondensation reaction. To incorporate the polyethylene terephthalate structural segment into the polyester backbone in a block state that is formed to some extent, polyethylene terephthalate can be added when the reaction percentage between the alcohol and carboxylic acid components is 10% or less, for example, 5% or less. The reaction percentage used herein is defined as: [Amount (mol) of liquid produced in the reaction] / [Amount (mol) of liquid assuming all components fully react]×100.

[0044] The polyethylene terephthalate structural segment contained in the amorphous resin A is preferably a repeating structure of a terephthalic acid and ethylene glycol condensate, represented by the following formula (6). In formula (6), p is preferably 3 or more and 10 or less, more preferably 4 or more and 8 or less. When p is in such a range, the ethylene glycol-derived structures of the polyethylene terephthalate structural segment contained in the amorphous resin A are advantageously localized to facilitate the easy formation of domains that improve the seepage of the release agent, resulting in an extended hot-offset resistance. The fact that the amorphous resin A contains the repeating structure of a terephthalic acid and ethylene glycol condensate, represented by formula (6), can be analyzed, for example, by time-of-flight secondary ion mass spectrometry (TOF-SIMS).where in formula (6) each * represents a bonding site of the polyester skeleton and. p represents an integer from 3 to 10.

[0045] Previously used polyethylene terephthalate (so-called recycled PET) can be used for the polyethylene terephthalate structural section in the amorphous resin A. The reuse of polyethylene terephthalate is desirable from an environmental perspective.

[0046] Previously used PET is collected. Collected PET is washed and then sorted to prevent mixing with other materials or waste. After labels and other contaminants are removed, the PET is shredded into flakes or similar particles. The shredded material can be used as is or kneaded into coarsely ground material. If chemical substances on the surface of the PET bottle cannot be sufficiently removed, alkaline washing can be applied. If alkaline washing results in partial hydrolysis of the shredded material, the washed shredded material can be melted and pelletized, and the resulting pellets are subjected to solid-phase polymerization to restore the reduced degree of polymerization.Solid-phase polymerization can be carried out continuously at a temperature of 180 °C to 245 °C, for example 200 °C to 240 °C, in an inert gas atmosphere, such as nitrogen or noble gas, using washed flakes or pellets formed by melt extrusion of the flakes. Alternatively, washed, comminuted material can be depolymerized into monomer units and subsequently resynthesized.

[0047] The recycled PET is not limited to the PET used as described above, and out-of-specification PET fiber waste and pellets rejected by factories may be used.

[0048] The monomers used to introduce at least one unit selected from the group consisting of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4) into the amorphous resin A include: 1,6-Hexanediol, 1,7-Heptanediol, 1,8-Octanediol, 1,9-Nonanediol, 1,10-Decanediol, 1,11-Undecanediol, 1,12-Dodecanediol, Suberic acid, Azelaic acid, Sebabic acid, Undecanedioic acid, Dodecanedioic acid, Hexadecanedioic acid, Octadecanedioic acid, Dodecenyl succinic acid, n-Octyl succinic acid, Isododecenyl succinic acid, Dodecenyl succinic acid, Isooctenyl succinic acid and Hexadecenyl succinic acid.

[0049] Of the units represented by formula (1), formula (2), formula (3), and formula (4), formula (1) and formula (2) are preferred. Since the alkyl or alkenyl group of these units, comprising 6 to 16 carbon atoms, branches off from the main chain of the polyester backbone, the affinity for the release agent described later is improved, further reducing bleed-through at the cleaning blade during printing in high-speed devices.

[0050] In addition to the structures and monomers described above, other components can also be used to produce the amorphous resin. Such components include polyhydric alcohols (dihydric or higher-hydric alcohols), polyvalent carboxylic acids (divalent or higher-hydric carboxylic acids), and their acid anhydrides or lower alkyl esters.

[0051] Polyhydric alcohols that can be used are as follows. Divalent alcohol components include ethylene glycol, polyethylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol, represented by formula (A), and their derivatives, and diols, represented by formula (B), where in formula (A) each R represents an ethylene or propylene group, x and y are each an integer of 0 or greater, and the average of x + y is 0 or greater and 10 or less. Where in formula (B) R' represents -CH2-CH2-, -CH2-CH(-CH3)-, or -CH2-C(-CH3)2-, x' and y' are each an integer of 0 or greater, and the average of x' + y' is 0 to 10.

[0052] Trivalent or higher-valent alcohol components include, for example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Glycerin, trimethylolpropane, and pentaerythritol can be used advantageously.

[0053] Dihydric alcohols and trihydric or higher-hydric alcohols can be used individually or in combination.

[0054] Divalent carboxylic acids include, for example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, azelaic acid, malonic acid, and their anhydrides and lower alkyl esters. Maleic acid, fumaric acid, and terephthalic acid can be used advantageously.

[0055] Trivalent or higher-valent carboxylic acids and their acid anhydrides or lower alkyl esters include, for example, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimeric acid, and their acid anhydrides or lower alkyl esters. Among these, 1,2,4-benzenetricarboxylic acid, i.e., trimellitic acid and its derivatives, are advantageously used due to their cost-effectiveness and ease of reaction control. Divalent carboxylic acids and trivalent or higher-valent carboxylic acids can be used individually or in combination.

[0056] Amorphous resin A can be prepared by any known method without limitation. For example, alcohol and carboxylic acid monomers, as mentioned above, are placed simultaneously in a vessel and polymerized by an esterification or transesterification reaction and a condensation reaction to produce a polyester. The polymerization temperature can be 180 °C or higher and 290 °C or lower, but is not limited to these temperatures. A polymerization catalyst can be used for the polymerization of the polyester unit. Examples include titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide. In some embodiments, amorphous resin A is a polyester prepared by polymerization using a tin-based catalyst.

[0057] Amorphous resin A can be a polyester with a vinyl polymer segment. To produce a polyester bonded to a vinyl polymer, a process can be used that employs a monomer component capable of reacting with both the vinyl polymer and the polyester. Such a monomer can be one containing an unsaturated double bond and a carboxyl or hydroxyl group. Examples include unsaturated dicarboxylic acids and their anhydrides, such as phthalic acid, maleic acid, and citraconic acid; and acrylic or methacrylic acid esters.

[0058] The peak molecular weight of the amorphous resin A according to the present disclosure is preferably 3,500 or more and 20,000 or less, for example from the point of view of low-temperature fixability. The glass transition temperature is preferably 40 °C to 70 °C.

[0059] In addition to the amorphous resin A described above, other amorphous resins, known as binder resins, can also be used in combination. Examples of such resins include phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleate resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron-indene resin, and petroleum-based resin. Release agent W

[0060] The wax used as release agent W is an ester wax. Any ester wax can be used without limitation, provided that the difference in SP value between amorphous resin A and release agent W, ΔSP value (SP A - SP W), which meets the requirement specified herein. Examples of such ester wax include monoester wax, which contains one ester bond in the molecule, diester wax, which contains two ester bonds in the molecule, and ester wax, which contains three or more ester bonds in the molecule.

[0061] Release agent W is preferably a monoester compound represented by formula (5). When release agent W is a monoester represented by formula (5), the long-chain hydrocarbon groups of the amorphous resin A, such as alkyl and alkenyl groups, and the two long-chain alkyl groups of the monoester compound intertwine to enhance their interaction, resulting in a more effective reduction of the release agent bleed-out phenomenon in high-speed devices. In formula (5), R3 and R4 each represent an alkyl group with 14 to 24 carbon atoms.

[0062] The monoester compound represented by formula (5) is produced by an esterification reaction between a long-chain fatty acid and an aliphatic alcohol.

[0063] Examples of long-chain fatty acids include pentadecanoic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, and lignoceric acid.

[0064] Examples of aliphatic alcohols include myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignoceryl alcohol.

[0065] The esterification reaction can be carried out at a reaction temperature of, for example, less than 250 °C and normal or reduced pressure, advantageously in an inert gas such as nitrogen. The proportion of the long-chain fatty acid and the aliphatic alcohol in the reaction can be suitably determined without limitation according to the purpose. Small amounts of esterification catalyst and solvent can be added to the esterification reaction.

[0066] Examples of the esterification catalyst include organo-titanium compounds, such as tetrabutoxytitanate and tetrapropoxytitanate; organo-tin compounds, such as butyltin dilaurate and dibutyltin oxide; organo-lead compounds; and sulfuric acid. Examples of the solvent include aromatic solvents, such as toluene, xylene, and petroleum ether.

[0067] The melting point of the release agent W is preferably 63 °C or higher and 78 °C or lower. The amount of release agent W is preferably 1.0 parts by mass to 10.0 parts by mass, relative to 100 parts by mass of the binder resin. Crystalline polyester

[0068] The toner disclosed herein preferably contains crystalline polyester. When the toner particles contain crystalline polyester, which exhibits high molecular mobility, the interaction between the crystalline polyester and amorphous resin A more advantageously localizes the ethylene glycol-derived structures within the polyethylene terephthalate structural region. Consequently, domains that enhance the seepage of the release agent are more likely to form, resulting in improved hot-offset resistance.

[0069] Monomers that can be used for the crystalline polyester include polyhydric alcohols (dihydric, trihydric or higher-hydric alcohols), polyvalent carboxylic acids (divalent, trivalent or higher-valent carboxylic acids), and their acid anhydrides or lower alkyl esters.

[0070] Examples of polyhydric alcohols include, but are not limited to, chain (advantageously linear) diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Linear α,ω-diols, such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, are considered advantageous.

[0071] The following polyhydric alcohols can also be used. Examples of dihydric alcohols include aromatic alcohols, such as polyoxyethylene-bisphenol A and polyoxypropylene-bisphenol A; and 1,4-cyclohexanedimethanol. Examples of trihydric or higher-hydric alcohols include aromatic alcohols, such as 1,3,5-trihydroxymethylbenzene; and chain alcohols, such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0072] Polyvalent carboxylic acids that can be used include, but are not limited to, chains (advantageously linear) of aliphatic dicarboxylic acids. Examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, their acid anhydrides, and hydrolysis products of lower alkyl esters.

[0073] The following polyvalent carboxylic acids can also be used. Divalent carboxylic acids include aromatic carboxylic acids, such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids, such as n-dodecyl succinic acid and n-dodecenyl succinic acid; alicyclic carboxylic acids, such as cyclohexanedicarboxylic acid; and their acid anhydrides and lower alkyl esters. Trivalent or higher-valent carboxylic acids include aromatic carboxylic acids, such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid. Aliphatic carboxylic acids, such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane; and their derivatives, such as acid anhydrides and lower alkyl esters.

[0074] The crystalline polyester used herein is preferably a modified crystalline polyester in which the hydroxyl group at one end of the main chain is modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or in which the carboxyl group at one end of the main chain is modified with an aliphatic monoalcohol having 15 to 30 carbon atoms. When the crystalline polyester is such a modified crystalline polyester, the long-chain alkyl group at one end of the main chain of the modified crystalline polyester and the long-chain alkyl group of the ester wax interact to enhance the reduction of the release agent's bleed-out phenomenon in high-speed devices.

[0075] Examples of aliphatic monocarboxylic acids with 16 to 31 carbon atoms include palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecanoic acid, arachidic acid (icosanoic acid), heneicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic acid.

[0076] Examples of aliphatic monoalcohols with 15 to 30 carbon atoms include cetyl alcohol, palmityl alcohol (hexadecanol), margaryl alcohol (heptadecanol), stearyl alcohol (octadecanol), nonadecanol, arachidyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, 1-heptacosanol, montanyl alcohol, 1-nonacosanol, and melissyl alcohol.

[0077] Crystalline polyester can be produced by conventional polyester synthesis. For example, crystalline polyester can be prepared by esterification or transesterification of a carboxylic acid and an alcohol, as described above, followed by conventional polycondensation under reduced pressure or in a nitrogen atmosphere. An aliphatic compound, as described above, is then added to the esterification to obtain the desired crystalline polyester.

[0078] In the esterification or transesterification reaction, a common esterification or transesterification catalyst, such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, can be used.

[0079] In the polycondensation reaction, a commonly known polycondensation catalyst, such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, or germanium dioxide, can also be used. The polymerization temperature and the amounts of catalysts can be determined as appropriate without limitation.

[0080] In esterification or transesterification, a process can be used in which all monomers are added at once to improve the strength of the resulting crystalline polyester. Alternatively, to reduce the low molecular weight components, divalent monomers can first be subjected to a reaction, and then trivalent or higher-valent monomers can be added.

[0081] The melting point of the crystalline polyester is preferably 70 °C to 110 °C, more preferably 80 °C to 100 °C, from the point of view of low-temperature fixability. In the toner disclosed herein, the amount of the crystalline polyester used is preferably 3 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the amorphous resin, from the point of view of low-temperature fixability and rub fastness and the maintenance of chargeability in a high-temperature, high-humidity environment. colorant

[0082] The toner particles may contain a colorant, if necessary. The following colorants can be used. The black colorant can be carbon black or a mixture whose color is adjusted to black using yellow, magenta, and cyan colorants. The colorant can be a pigment alone or a combination of pigment and colorant. From the standpoint of full-color image quality, pigment and colorant are preferably used in combination.

[0083] Pigments for magenta toners include CI Pigment Reds 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 Reds 1, 2, 10, 13, 15, 23, 29, and 35.

[0084] Colorants for magenta toners include oil-soluble colorants such as CI Solvent Reds 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109 and 121, CI Disperse Red 9, CI Solvent Violets 8, 13, 14, 21 and 27 and CI Disperse Violet 1; and basic colorants, such as CI Basic Reds 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 Violets 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0085] Pigments for cyan toners 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 pigment, which has a phthalocyanine backbone substituted with one to five phthalimidomethyl groups. CI Solvent Blue 70 can also be used as a colorant for cyan toners.

[0086] Pigments for yellow toners include CI Pigment Yellows 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185 and CI Vat Yellows 1, 3 and 20. CI Solvent Yellow 162 can also be used as a colorant for yellow toners.

[0087] Colorants can be used individually or can be mixed for use and can also be used in a mixed crystal state.

[0088] The colorant is selected taking into account hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersion among the toner particles.

[0089] The amount of colorant is preferably 0.1 parts by mass to 30.0 parts by mass, relative to 100 parts by mass of the binder resin. Charge control agent

[0090] The toner particles may contain a charge control agent, if required. When added, the charge control agent stabilizes the charge on the toner particles and enables optimal control of the frictional charge according to the development system. Known charge control agents can be used, particularly colorless aromatic carboxylic acid-metal compounds, which allow the toner to be charged quickly and a constant charge level to be maintained.

[0091] Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds with sulfonic acid or carboxylic acid side chains, polymeric compounds with sulfonic acid salt or ester side chains, polymeric compounds with carboxylic acid salt or ester side chains, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0092] The charge control agent can be added within the toner particles or externally to the toner particles. The amount of charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass, more preferably 0.5 parts by mass to 10.0 parts by mass, relative to 100 parts by mass of the binder resin. Inorganic fine particles

[0093] The toner may contain inorganic particles, if required. These inorganic particles can be incorporated within the toner particles or mixed with the toner as an external additive. Examples of such inorganic particles include silica particles, titanium oxide particles, aluminum oxide particles, and their complex oxide particles. Silica and titanium oxide particles are advantageous for improving the toner's flowability and uniform charge. The inorganic particles are preferably hydrophobized with a water-repellent agent, such as a silane compound, silicone oil, or a mixture thereof. External additive

[0094] Other external additives besides the inorganic fine particles mentioned above can be used, such as melamine resin fine particles, polytetrafluoroethylene resin fine particles, and other organic fine particles.

[0095] From the point of view of improving flowability, the mean diameter (D50) of the external additive is preferably 10 nm or more on a numerical basis and is also preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 90 nm or less.

[0096] The external additive content is preferably 0.1 parts by mass to 10.0 parts by mass relative to 100 parts by mass of the toner particles. A known mixer, such as a Henschel mixer, can be used to mix the toner particles with the external additive. developer

[0097] The toner disclosed herein can be used as a single-component developer, but can be mixed with a magnetic carrier as a two-component developer to improve dot reproducibility in order to continuously provide images over a long period of time.

[0098] The magnetic support can be selected from known magnetic materials, and examples include iron oxide; metal particles of iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium or rare earth metals, their alloying particles, and their oxide particles; ferrite or the like; and magnetic material dispersion resin supports (which are called resin supports) containing a magnetic material and a binder resin that keeps the magnetic material dispersed.

[0099] When the toner is mixed with a magnetic carrier to be used as a two-component developer, the toner content in the two-component developer is preferably 2% by mass to 15% by mass, for example 4% by mass to 13% by mass. Manufacturing process for toner particles

[0100] The toner particles can be produced without limitation by known methods such as pulverization, suspension polymerization, dissolution suspension, emulsion aggregation, and dispersion polymerization. In some embodiments, a pulverization method is used to control the release agent on the surface of the toner particles. Therefore, the toner particles are preferably pulverized. One procedure of the pulverization process for producing the toner is now described.

[0101] The pulverization process includes a raw material mixing step of mixing, for example, ester wax as the release agent, binder resin comprising amorphous resin A and crystalline polyester, and optional components such as other amorphous resin, a colorant, and a charge control agent; a step of melting and kneading the mixture of raw materials to prepare a resin composition; and a step of pulverizing the resulting resin composition into toner particles.

[0102] In the raw material mixing step, toner materials, such as binder resin, wax, and optional components like a colorant and a charge control agent, are mixed in predetermined ratios. Examples of mixing devices used in this step include double-cone mixers, V-shaped mixers, drum mixers, super mixers, Henschel mixers, Nauta mixers, and the Mechano Hybrid, manufactured by Nippon Coke & Engineering.

[0103] The mixture is then melt-kneaded to disperse the materials in the binder resin. A batch-type kneading machine, such as a pressure kneader or a Banbury mixer, or a continuous kneading machine can be used in the melt-kneading step. Single-screw or twin-screw extruders are common because of the advantage of enabling continuous production. Examples include the KTK twin-screw extruder, manufactured by Kobe Steel; the TEM twin-screw extruder, manufactured by Toshiba Machine; the PCM kneader, manufactured by Ikegai; the twin-screw extruder, manufactured by KCK; the Co-kneader, manufactured by Buss; and the Kneadex, manufactured by Nippon Coke & Engineering. The resin composition obtained by melt-kneading can further be rolled using a two-roll mill or similar equipment and cooled with water in a cooling step.

[0104] The cooled resin composition is pulverized into particles of a desired size. In the pulverization step, the resin composition is coarsely ground, for example, using a crusher, hammer mill, spring mill, or similar equipment.

[0105] The crushed resin composition is then finely pulverized using a pulverizer, such as a Kryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering), a turbo mill (manufactured by Freund Turbo) or an air jet pulverizer.

[0106] If necessary, the resulting pulverized resin composition can be classified using a classifier or a sifter, such as an inertial classifier Elbow-Jet (Nittetsu Mining), a centrifugal classifier Turboplex (manufactured by Hosokawa Micron), TSP Separator (manufactured by Hosokawa Micron), or Faculty (manufactured by Hosokawa Micron).

[0107] Subsequently, if required, an external additive, such as silica particles, can be added to the surface of the toner particles, thus producing the toner. A mixing device can be used for adding the external additive, and examples include double-cone mixers, V-shaped mixers, drum mixers, super mixers, Henschel mixers, Nauta mixers, Mechano Hybrid (manufactured by Nippon Coke & Engineering), and Nobilta (manufactured by Hosokawa Micron).

[0108] The methods for measuring the physical properties are now described. Separation of materials from toner

[0109] The toner materials can be separated from each other using the differences in their solubilities in a solvent or by gel permeation chromatography (GPC). The separated materials are used to measure their physical properties, as described below.

[0110] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23 °C to separate it into soluble components (amorphous resin A, amorphous resin B and crystalline polyester) and insoluble components (release agent W, colorant, inorganic fine particles, and others).

[0111] Second separation: The soluble components (amorphous resin A, amorphous resin B and crystalline polyester) obtained by the first separation are dissolved in tetrahydrofuran (THF) at 23 °C to separate into soluble components (amorphous resin A and amorphous resin B) and an insoluble component (crystalline polyester).

[0112] Third separation: The insoluble components (release agent W, colorant, inorganic fine particles and others) obtained by the first separation are dissolved in MEK at 100 °C to separate them into a soluble component (release agent W) and insoluble components (colorant, inorganic fine particles and others).

[0113] Fourth separation: The soluble components (amorphous resin A and amorphous resin B) obtained by the second separation are dissolved in tetrahydrofuran (THF) at 23 °C and separated into amorphous resin A and amorphous resin B by preparative gas-phase chromatography (GPC). Methods for confirming the assignment of different monomer units in amorphous resin and crystalline polyesters and methods for measuring the content of the monomer units

[0114] The confirmation of the assignment of different monomer units in an amorphous resin and a crystalline polyester and the measurement of the content of the monomer units are carried out by means of 1 H-NMR was performed under the following conditions. Measuring device: FT-NMR, JNM-EX400 (manufactured by JEOL) Measurement frequency: 400 MHz Pulse width: 5.0 µs Frequency range: 10500 Hz Number of scans: 64 Measurement temperature: 30 °C Sample: A sample is prepared by placing 50 mg of a measurement sample into a sample tube with an inner diameter of 5 mm, adding deuterated chloroform (CDCl3) as a solvent, and dissolving this measurement sample in a thermostatic chamber at 40 °C.

[0115] The structures of different monomer units are derived from the obtained 1 H-NMR diagram specified, and the integral values ​​S1, S2, S3, ... and S n The peaks that are assigned to the monomer units are calculated.

[0116] The content of each monomer unit is determined using the integral value S1, S2, S3, ... and S n as follows. It should be noted that n1, n2, n3, ..., and n n each represents the number of hydrogen atoms in the respective monomer units. Content of each monomer unit (mol-%)={(Sn / nn) / ((S1 / n1)+(S2 / n2)+(S3 / n3)…+(Sn / nn))}×100

[0117] The numerator term of a similar operation is modified, and the content (mol%) of each monomer unit is calculated. If a polymerizable monomer that does not contain hydrogen atoms is used as the monomer unit, 13 C-NMR measurement, in which the nucleus to be measured 13C is performed in a single-pulse mode, and the calculation is performed in the same way by 1 ¹H NMR was performed. Calculation of the SP values ​​of amorphous resins, crystalline polyester, and release agents. The SP values ​​of amorphous resins, crystalline polyesters and release agents are calculated according to the method proposed by Fedors.

[0118] Specifically, for each of these materials, the evaporation energy (Δei), molar volume (Δvi) and molar ratio (j) of each monomer unit in the material are determined, and the SP value is calculated using these values ​​by the following equation: SP−value(cal / cm3)0.5={(∑j×∑Δei) / (∑j×∑Δvi)}0.5

[0119] The values ​​given in "Polym. Eng. Sci., 14(2), 147-154 (1974)" are used for the vaporization energy (Δei) and molar volume (Δvi) of the atoms or atomic groups in each monomer unit. Measurement of the glass transition temperatures Tg of toner and amorphous resins

[0120] The glass transition temperatures Tg of the toner and the amorphous resins are measured according to ASTM D3418-82 using a Q2000 differential scanning calorimeter (manufactured by TA Instruments). Temperature correction of the calorimeter detector is performed using the melting points of indium and zinc, and heat correction is performed using the heat of fusion of indium. Specifically, approximately 3 mg of toner or amorphous resin is weighed out and placed in an aluminum dish. The sample is measured under the following conditions, using an empty aluminum dish as a reference. Heating rate 10 °C / min Measurement start temperature 30 °C Measurement end temperature 180 °C

[0121] The measurement is performed in the temperature range of 30 °C to 180 °C at a heating rate of 10 °C / min. The sample is heated once to 180 °C and held at this temperature for 10 minutes. It is then cooled to 30 °C and reheated at a heating rate of 10 °C / min. During the second heating, a change in specific heat occurs in the range of 30 °C to 100 °C. The glass transition temperatures Tg of the toner and amorphous resin are each defined as the intersection of the line at the midpoint between the baselines before and after the change in specific heat at that time and the differential thermal curve. GPC measurement of the weight-averaged molecular weight Mw of the amorphous resin.

[0122] The molecular weight (Mw) of the THF-soluble fraction of the amorphous resin is measured by gel permeation chromatography (GPC) as follows.

[0123] First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is filtered through a solvent-resistant Maishori Disk membrane filter with a pore size of 0.2 µm (manufactured by Tosoh Corporation) to obtain a sample solution. The sample solution is adjusted to a THF-soluble concentration of approximately 0.8 wt%. The resulting sample solution is measured under the following conditions: Device: HLC-8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Columns: Combination of 7 columns from the Shodex series KF-801, KF-802, KF-803, KF-804, KF-805, KF-806 and KF-807 (manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Oven temperature: 40.0 °C Volume of injected sample: 0.10 mL

[0124] To calculate the molecular weight of the sample, a molecular weight calibration curve is created using standard polystyrene resins (for example, 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, manufactured by Tosoh Corporation). GPC measurement of the weight-averaged molecular weight of crystalline polyester

[0125] The molecular weight (Mw) of the toluene-soluble fraction of the crystalline polyester at 100 °C is measured by gel permeation chromatography (GPC) as follows.

[0126] First, the crystalline polyester resin is dissolved in toluene at 100 °C for one hour. The resulting solution is filtered through a solvent-resistant Maishori Disk membrane filter with a pore size of 0.2 µm (manufactured by Tosoh Corporation) to obtain a sample solution. The sample solution is adjusted to a toluene-soluble content of approximately 0.1 wt%. The resulting sample solution is measured under the following conditions: device HLC-8121 GPC / HT (manufactured by Tosoh Corporation) column TSK-G el GMHHR-H HT (7.8 cm ID × 30 cm), combination of two columns (manufactured by Tosoh Corporation) detector High-temperature RI temperature 135 °C solvent toluene flow rate 1.0 mL / min sample Injection of 0.4 mL of a 0.1% sample

[0127] To calculate the molecular weight of the sample, a molecular weight calibration curve generated using monodisperse polystyrene standards is employed. Additionally, a conversion equation derived from the Mark-Houwink viscosity equation is used to calculate the molecular weight in terms of polyethylene. Identification and molecular weight measurement of release agent W by pyrolysis-GC-MS Mass spectrometer ISQ, manufactured by Thermo Fisher Scientific GC analyzer Focus GC, manufactured by Thermo Fisher Scientific Ion source temperature 250 °C Ionization Electron ionization (EI) mass range 50 m / s to 1000 m / s column HP-5MS(30 m) Pyrolysator JPS-700, manufactured by Japan Analytical Industry

[0128] The separating agent W, which was separated from the toner, and 1 µl of tetramethylammonium hydroxide (TMAH) are placed on a pyrolytic foil at 590 °C. The prepared sample is subjected to pyrolysis-GC-MS under the conditions described above to obtain the peaks of the alcohol and carboxylic acid components derived from the ester. Due to TMAH acting as a methylating agent, the alcohol and carboxylic acid components are detected in methylated forms. The structure of the wax is identified by analyzing the obtained peaks. Measurement of the peak melting temperature (melting point) T C (°C) of crystalline polyester and the like

[0129] The melting point (T C The viscosity of crystalline polyester is measured according to ASTM D3418-82 using a Q2000 differential scanning calorimeter (manufactured by TA Instruments).

[0130] The temperature correction of the calorimeter detector is performed using the melting points of indium and zinc, and the heat correction is performed using the latent heat of fusion of indium. Specifically, 3 mg of a sample are weighed out and placed in an aluminum dish. The sample is then measured under the following conditions, using an empty aluminum dish as a reference. Heating rate 10 °C / min Measurement start temperature 30 °C Measurement end temperature 180 °C

[0131] The measurement will be performed in the temperature range of 30 °C to 180 °C at a heating rate of 10 °C / min. The sample will be heated once to 180 °C and held at this temperature for 10 minutes. It will then be cooled to 30 °C and reheated. The temperature in the range of 30 °C to 100 °C during the second heating, at which the highest endothermic peak appears in the temperature-endothermic curve, is defined as the melting point. EXAMPLES

[0132] The implementation of this disclosure is described in detail with reference to the following examples and comparative examples. However, it is not limited to these examples. In the following formulations, unless otherwise specified, "part(s)" refers to a mass basis. Production example of amorphous resin A1 - Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1): 20.9 parts (42.0 mol−%) - Bisphenol A-propylene oxide adduct (average number of moles of added propylene oxide: 2.0 mol): 47.4 parts (29.0 mol−%) - Terephthalic acid: 15.8 parts (18.3 mol%) - Dodecenyl succinic acid: 15.8 parts (10.6 mol%) - Titanium tetrabutoxide (esterification catalyst): 0.5 parts - Gallic acid (promoter): 0.1 parts

[0133] The above components were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet and a thermocouple.

[0134] The molar percentage of polyethylene terephthalate was calculated using the total number of units derived from ethylene glycol and terephthalic acid.

[0135] After the reaction vessel was purged with nitrogen gas, the contents of the reaction vessel were gradually heated while stirring and allowed to react for 2 hours at 200 °C while stirring.

[0136] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for a further 5 hours at a constant temperature of 200 °C. After confirmation that the weight-averaged molecular weight had reached 6700, the reaction was stopped by lowering the temperature, yielding amorphous resin A1 containing a polyethylene terephthalate structural segment in the molecule. The physical properties of the resulting amorphous resin A1 are shown in Table 1-1. Production of amorphous resins A2 to A18

[0137] The amorphous resins A2 to A18, which contain a polyethylene terephthalate structural segment in the molecule, were prepared by a reaction carried out in the same manner as in the preparation example of amorphous resin A1, except that the types and amounts of polyethylene terephthalate and polymerizable monomers were modified as shown in Tables 1-1 to 1-3. The physical properties of the resulting amorphous resins A2 to A18 are shown in Tables 1-1 to 1-3. Production of the amorphous resin A19 - Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1): 41.3 parts (49.3 mol−%) - Diethylene glycol: 28.4 parts (32.5 mol%) - Isophthalic acid: 2.9 parts (2.0 mol%) - Dodecenyl succinic acid: 14.4 parts (5.9 mol%) - Adipic acid: 13.0 parts (10.3 mol%) - Titanium tetrabutoxide (esterification catalyst): 0.5 parts - Gallic acid (promoter): 0.1 parts

[0138] The above components were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet and a thermocouple.

[0139] The molar percentage of polyethylene terephthalate was calculated using the total number of units derived from ethylene glycol and terephthalic acid.

[0140] After the reaction vessel was purged with nitrogen gas, the contents of the reaction vessel were gradually heated while stirring and allowed to react for 2 hours at 200 °C while stirring.

[0141] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for a further 5 hours at a constant temperature of 200 °C. After confirmation that the weight-averaged molecular weight had reached 6700, the reaction was stopped by lowering the temperature, yielding the amorphous resin A19, which contained a polyethylene terephthalate structural segment in the molecule. Amorphous resin A19 was subjected to physical property measurements using the procedures described above and exhibited a SP value of 11.17 (cal / cm³). 3 ) 0,5 , W EG of 24.6 mol-%, W CH of 5.9 mol% and a Tg of 58.0 °C. Table 1-1 Amorphous resin A1 Amorphous resin A2 Amorphous resin A3 Amorphous resin A4 Amorphous resin A5 Amorphous resin A6 parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% Polyethylene terephthalate 20,9 42,0 18,6 38,1 19,1 39,0 22,7 44,1 23,3 44,8 25,6 48,3 alcohol component BPA-PO 47,4 29,0 47,7 30,3 45,7 28,9 49,5 29,8 50,7 30,2 38,8 22,8 Carboxylic acid component Terephthalic acid 15,8 18,3 15,9 19,1 15,2 18,2 16,5 18,8 16,9 19,0 12,9 14,4 Dodecenyl succinic acid 15,8 10,6 17,9 12,5 20,0 13,9 11,3 7,5 9,1 6,0 22,7 14,6 Tetradecanedioic acid Suberic acid Octadecanedioic acid Adipic acid Eicosandhioic acid Physical property SP 11,30 11,25 11,25 11,36 11,38 11,38 W EG 21,4 19,0 19,4 22,0 22,4 24,0 W CH 10,6 12,5 14,0 7,5 6,0 14,6 Tg 45,3 40,5 39,8 54,8 55,5 40,5 Mw 6700 6700 6700 6700 6700 6700 Table 1-2 Amorphous resin A7 Amorphous resin A8 Amorphous resin A9 Amorphous resin A10 Amorphous resin A11 Amorphous resin A12 parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% Polyethylene terephthalate 24,5 47,0 12,2 27,1 11,7 26,0 11,2 25,4 25,5 48,0 21,8 46,8 alcohol component BPA-PO 38,2 22,7 60,3 41,3 61,8 42,6 53,6 37,6 44,6 26,0 56,5 37,5 Carboxylic acid component Terephthalic acid 12,7 14,3 20,1 26,1 20,6 26,9 17,9 23,7 14,9 16,4 Dodecenyl succinic acid 24,5 16,0 7,4 5,6 6,0 4,5 17,4 13,4 15,0 9,6 21,6 15,8 Tetradecanedioic acid Suberic acid Octadecanedioic acid Adipic acid Eicosandhioic acid Physical property SP 11,35 11,16 11,16 11,10 11,41 10,80 W EG 23,5 13,5 13,0 12,7 24,8 23,4 W CH 16,0 5,6 4,5 13,4 9,6 15,8 Tg 39,8 54,8 55,5 42,3 48,2 41,8 Mw 6700 6700 6700 6700 6700 6700 Table 1-3 Amorphous resin A13 Amorphous resin A14 Amorphous resin A15 Amorphous resin A16 Amorphous resin A17 Amorphous resin A18 parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% parts Mol-% Polyethylene terephthalate 27,0 49,9 22,2 42,6 23,7 45,5 21,7 37,1 23,0 44,9 20,9 40,9 alcohol component BPA-PO 43,8 25,1 60,2 35,8 46,9 27,9 62,6 37,4 52,2 31,1 47,4 28,3 Carboxylic acid component Terephthalic acid 14,6 15,8 8,5 9,6 15,6 17,6 0,3 0,3 17,4 19,6 15,8 17,8 Dodecenyl succinic acid 14,6 9,2 Tetradecanedioic acid 15,8 13,0 Suberic acid 9,1 12,0 Octadecanedioic acid 13,8 9,1 Adipic acid 15,4 19,9 Eicosandhioic acid 7,4 4,4 Physical property SP 11,44 11,13 11,23 11,30 11,29 11,21 AWAY 25,0 22,0 22,5 18,8 22,8 20,9 W CH 9,2 12,0 10,0 - - 13,0 Tg 49,1 48,5 45,9 49,1 45,6 45,3 Mw 6700 6700 6700 6700 6700 6700

[0142] The abbreviations in Tables 1-1 to 1-3 are as follows. BPA-PO: Bisphenol A-propylene oxide adduct (average number of moles of added propylene oxide: 2.0 mol) Production of amorphous resin B1 - Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1): 4.1 parts (9.8 mol%) - Bisphenol A-propylene oxide adduct (average number of moles of added propylene oxide: 2.0 mol): 57.8 parts (42.8 mol%) - Terephthalic acid: 29.9 parts (41.9 mol%) - Trimellitic acid: 7.0 parts (4.5 mol%) - Stearic acid: 1.2 parts (1.0 mol%)

[0143] The materials described above were weighed and placed in a sufficiently heated and dried reaction vessel equipped with a stirrer. To 100 parts by mass of this mixture, 0.5 parts by mass of tin(II) 2-ethylhexanoate (esterification catalyst) and 0.1 parts by mass of gallic acid (promoter) were added. The reaction vessel was heated to 260 °C while maintaining an inert atmosphere by introducing nitrogen gas into the vessel, thereby synthesizing the amorphous resin B1.

[0144] NMR analysis of the resulting amorphous resin B1 revealed that it contained 4.9 mol% of ethylene glycol-derived monomer units, 46.8 mol% of terephthalic acid-derived monomer units, 42.8 mol% of a monomer unit derived from a bisphenol A-propylene oxide adduct (average number of moles of added propylene oxide: 2.0 mol), 4.5 mol% of a trimellitic acid-derived monomer unit, and 1.0 mol% of a stearic acid-derived monomer unit. Amorphous resin B1 was subjected to physical property measurements using the methods described above and exhibited a SP value of 11.54 (cal / cm²). 3 ) 0,5 , W EG of 4.9 mol% and a Tg of 74.7 °C. Production of crystalline polyester C1 - Ethylene glycol: 10.2 parts (48.2 mol%) - Tetradecanedioic acid: 81.3 parts (48.3 mol%) - Behenic acid: 8.5 parts (3.5 mol%) - Titanium tetrabutoxide (esterification catalyst): 0.5 parts

[0145] The above components were weighed and placed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet and a thermocouple.

[0146] After the reaction vessel was purged with nitrogen gas, the contents of the reaction vessel were gradually heated while stirring and allowed to react for 2 hours at 200 °C while stirring.

[0147] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for another 5 hours at a constant temperature of 200 °C. The reaction was then stopped by lowering the temperature to obtain crystalline polyester C1. The resulting crystalline polyester C1 had a weight-average molecular weight (Mw) of 18,000 and a melting point (Tc) of 92 °C.

[0148] The NMR analysis of the resulting crystalline polyester C1 revealed that the crystalline polyester contained 48.2 mol% of ethylene glycol-derived monomer units, 48.3 mol% of tetradecanedioic acid-derived monomer units, and 3.5 mol% of behenic acid-derived monomer units.

[0149] The SP value of the crystalline polyester C1 was 10.09 (cal / cm³). 3 ) 0,5 The physical properties of the crystalline polyester C1 are shown in Table 2. Production of crystalline polyesters C2 to C5

[0150] Crystalline polyesters C2 to C5 were prepared by a reaction carried out in the same manner as for the preparation of crystalline polyester C1, except that the types and amounts of polymerizable monomers and aliphatic monocarboxylic acids or aliphatic monoalcohols were modified as shown in Table 2. The physical properties of amorphous polyesters C2 to C5 are shown in Table 2. Table 2 Crystalline Polyester C1 Crystalline Polyester C2 Crystalline Polyester C3 Crystalline Polyester C4 Crystalline Polyester C5 parts Mole % parts Mole % parts Mole % parts Mole % parts Mole % alcohol component Ethylene glycol (number of carbon atoms: 2) 10,2 48,2 10,2 47,6 10,2 47,5 10,1 48,5 10,1 48,7 Carboxylic acid component Tetradecanedioic acid 81,3 48,3 81,3 47,7 81,3 47,5 81,1 48,6 81,1 48,7 Aliphatic monocarboxylic acid Behenic acid (number of carbon atoms: 22) 8,5 3,5 Palmitic acid (number of carbon atoms: 16) 8,5 4,7 Pentadecanoic acid (number of carbon atoms: 15) 8,5 5,0 Montanic acid (number of carbon atoms: 28) 8,8 2,9 Lacceric acid (number of carbon atoms: 32) 8,8 2,6 Physical property SP 10,09 10,11 10,12 10,09 10,08 Tc 92,0 90,0 89,0 94,0 95,0 Mw 18000 18000 18000 18000 18000

[0151] Production example for toner 1 - Amorphous resin A1: 66 parts - Amorphous resin B1: 34 parts - crystalline polyester C1: 10 parts - Behenyl behenate (monoester wax): 5 parts - Soot: 5 parts

[0152] The materials described above were thoroughly mixed using a Henschel mixer (FM-75, manufactured by Nippon Coke & Engineering) at a rotational speed of 1500 rpm for 5 minutes. The mixture was then kneaded in a twin-screw mixer (PCM-30, manufactured by Ikegai) at a set temperature of 130 °C. The kneaded product was cooled and coarsely ground to 1 mm or less using a hammer mill. The resulting ground product was further pulverized to even smaller particle sizes using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo). Finally, the pulverized product was classified using Faculty (F-300, manufactured by Hosokawa Micron) to obtain toner particles 1. The operating conditions were set to a classifying rotor speed of 11,000 rpm and a dispersion rotor speed of 7,200 rpm. - Toner particles 1: 95 parts - Larger inorganic fine particles: pyrogenic silica, surface-treated with hexamethyldisilazane (number-averaged median diameter (D50) 120 nm): 4 parts - Smaller inorganic fine particles: Titanium oxide fine particles, surface-treated with isobutyl(trimethoxy)silane (number-averaged median diameter (D50) 10 nm): 1 part

[0153] The materials shown above were mixed for 10 minutes at a rotational speed of 1900 rpm using a Henschel mixer (FM-75, manufactured by Nippon Coke & Engineering) to obtain a negatively chargeable toner 1. The volume-averaged particle size of toner 1 was 6.6 µm.

[0154] Toner 1 was separated into amorphous resin A, crystalline polyester C, and release agent W according to the procedure described above, and the NMR analysis of the separated components yielded results consistent with the values ​​given in Tables 1-1 to 1-3 and 2. The formulation and physical properties of the resulting toner 1, obtained according to the procedures described above, are presented in Tables 3-1 and 3-2. Manufacturing examples for toner 2 to 32

[0155] Toners 2 to 32 were prepared in the same manner as in the preparation example for toner 1, except that the types and quantities of amorphous resin A, crystalline polyester C, and release agent W were modified as shown in Tables 3-1 and 3-2. The physical properties of the resulting toners are shown in Tables 3-1 and 3-2. The release agents W used in toners 2 to 32 are specified in Table 4. Table 3-1 toner Formulation / Physical Property Amorphous resin A Amorphous resin B crystalline polyester C Release agent W SP A -SP W W EG W CH IN W / IN CH IN CH / IN EG Tg Art Art parts Art Art Art Art parts - Mole % Mole % - - 1 1 66 1 1 1 Monoester 5,0 2,71 21,4 10,6 0,47 0,50 55,3 2 2 66 1 1 1 Monoester 5,0 2,66 19,0 12,5 0,40 0,66 55,3 3 3 66 1 1 1 Monoester 7,0 2,66 19,4 14,0 0,50 0,72 54,8 4 4 66 1 1 1 Monoester 3,4 2,77 22,0 7,5 0,45 0,34 57,2 5 5 66 1 1 1 Monoester 3,0 2,79 22,4 6,0 0,50 0,27 57,5 6 1 66 1 1 1 Monoester 2,2 2,71 21,4 10,6 0,21 0,50 56,9 7 1 66 1 1 1 Monoester 1,8 2,71 21,4 10,6 0,17 0,50 56,4 8 1 66 1 1 1 Monoester 7,3 2,71 21,4 10,6 0,69 0,50 56,1 9 1 66 1 1 1 Monoester 8,0 2,71 21,4 10,6 0,75 0,50 55,5 10 1 66 1 1 2 Monoester 5,0 2,72 21,4 10,6 0,47 0,50 54,2 11 1 66 1 1 3 Monoester 5,0 2,70 21,4 10,6 0,47 0,50 55,8 12 6 66 1 1 1 Monoester 5,0 2,79 24,0 14,6 0,34 0,61 55,6 13 7 66 1 1 1 Monoester 5,0 2,76 23,5 16,0 0,31 0,68 55,1 14 8 66 1 1 1 Monoester 3,5 2,57 13,5 5,6 0,63 0,41 57,1 15 9 66 1 1 1 Monoester 3,0 2,57 13,0 4,5 0,67 0,35 58,3 16 10 66 1 1 1 Monoester 5,0 2,51 12,7 13,4 0,37 1,06 53,3 17 11 66 1 1 1 Monoester 5,0 2,82 24,8 9,6 0,52 0,39 57,9 18 1 66 1 1 4 Polyvalent Ester 5,0 2,49 21,4 10,6 0,47 0,50 55,2 19 12 66 1 1 5 Polyvalent Ester 5,0 1,90 23,4 15,8 0,32 0,68 52,9 20 13 66 1 1 6 Monoester 5,0 2,85 25,0 9,2 0,54 0,37 57,8 21 14 66 1 1 1 Monoester 5,0 2,54 22,0 12,0 0,42 0,55 56,0 22 15 66 1 1 1 Monoester 5,0 2,64 22,5 10,0 0,50 0,44 56,6 23 18 66 1 1 1 Monoester 5,0 2,62 20,9 13,0 0,38 0,62 49,8 24 1 66 1 2 1 Monoester 5,0 2,71 21,4 10,6 0,47 0,50 55,3 25 1 66 1 3 1 Monoester 5,0 2,71 21,4 10,6 0,47 0,50 55,3 26 1 66 1 4 1 Monoester 5,0 2,71 21,4 10,6 0,47 0,50 55,3 27 1 66 1 5 1 Monoester 5,0 2,71 21,4 10,6 0,47 0,50 55,3 28 1 66 1 1 7 Amide wax 5,0 1,30 21,4 10,6 0,47 0,50 56,9 29 1 66 1 1 8 hydrocarbon wax 5,0 3,02 21,4 10,6 0,47 0,50 55,9 30 16 66 1 1 1 Monoester 5,0 2,71 18,8 - - - 49,2 31 17 66 1 1 1 Monoester 5,0 2,70 22,8 - - - 58,5 32 19 66 1 1 1 Monoester 5,0 2,58 24,6 5,9 0,85 0,24 59,5 Table 3-2 toner Formulation / Physical Property Amorphous resin A Amorphous resin B crystalline polyester C Release agent W M EG M CH W W / M CH Art Art parts Art Art Art Art parts mol / kg mol / kg 1 1 66 1 1 1 Monoester 5,0 0,63 0,31 16,1 2 2 66 1 1 1 Monoester 5,0 0,53 0,34 14,7 3 3 66 1 1 1 Monoester 7,0 0,53 0,38 18,4 4 4 66 1 1 1 Monoester 3,4 0,65 0,22 15,5 5 5 66 1 1 1 Monoester 3,0 0,68 0,18 16,7 6 1 66 1 1 1 Monoester 2,2 0,64 0,32 6,9 7 1 66 1 1 1 Monoester 1,8 0,64 0,32 5,6 8 1 66 1 1 1 Monoester 7,3 0,61 0,31 23,5 9 1 66 1 1 1 Monoester 8,0 0,61 0,30 26,7 10 1 66 1 1 2 Monoester 5,0 0,63 0,31 16,1 11 1 66 1 1 3 Monoester 5,0 0,63 0,31 16,1 12 6 66 1 1 1 Monoester 5,0 0,72 0,44 11,4 13 7 66 1 1 1 Monoester 5,0 0,70 0,48 10,4 14 8 66 1 1 1 Monoester 3,5 0,35 0,15 23,3 15 9 66 1 1 1 Monoester 3,0 0,34 0,12 25,0 16 10 66 1 1 1 Monoester 5,0 0,32 0,34 14,7 17 11 66 1 1 1 Monoester 5,0 0,73 0,29 17,2 18 1 66 1 1 4 Polyvalent Ester 5,0 0,63 0,31 16,1 19 12 66 1 1 5 Polyvalent Ester 5,0 0,63 0,42 11,9 20 13 66 1 1 6 Monoester 5,0 0,77 0,28 17,9 21 14 66 1 1 1 Monoester 5,0 0,64 0,35 14,3 22 15 66 1 1 1 Monoester 5,0 0,68 0,30 16,7 23 18 66 1 1 1 Monoester 5,0 0,57 0,34 14,7 24 1 66 1 2 1 Monoester 5,0 0,63 0,31 16,1 25 1 66 1 3 1 Monoester 5,0 0,63 0,31 16,1 26 1 66 1 4 1 Monoester 5,0 0,63 0,31 16,1 27 1 66 1 5 1 Monoester 5,0 0,63 0,31 16,1 28 1 66 1 1 7 Amide wax 5,0 0,63 0,31 16,1 29 1 66 1 1 8 hydrocarbon wax 5,0 0,63 0,31 16,1 30 16 66 1 1 1 Monoester 5,0 0,64 - - 31 17 66 1 1 1 Monoester 5,0 0,68 - - 32 19 66 1 1 1 Monoester 5,0 1,18 0,28 17,9 Table 4 Release agent W Art Art R3 Number of carbon atoms R4 Number of carbon atoms SP W 1 Monoester 21 22 8,59 2 Monoester 14 15 8,58 3 Monoester 23 24 8,60 4 Polyvalent Ester - - 8,81 5 Polyvalent Ester - - 8,90 6 Monoester 22 23 8,59 7 Amide wax - - 10,00 8 hydrocarbon wax - - 8,28

[0156] The separating agents 1, 2, 3, and 6 in Table 4 are ester compounds represented by formula (5). In Table 4, “R3 number of carbon atoms” means “the number of carbon atoms in the alkyl group of R3 in formula (5)”, and “R4 number of carbon atoms” means “the number of carbon atoms in the alkyl group of R4 in formula (5)”. The separating agents 4, 5, 7, and 8 in Table 4 have the following structures: hydrocarbon wax with a number-averaged molecular weight of 675 Manufacturing example of magnetic carrier 1 - Magnetite 1 with a number-averaged particle size of 0.30 µm (magnetization intensity of 65 Am) 2 / kg under a magnetic field of 1000 / 4n (kA / m) - Magnetite 2 with a number-averaged particle size of 0.50 µm, (magnetization intensity of 65 Am 2 / kg under a magnetic field of 1000 / 4n (kA / m)

[0157] The fine particles of each of the above magnetites were treated by adding 4.0 parts of a silane compound (3-(2-Aminoethylamino)propyltrimethoxysilane) to 100 parts of the fine particles and stirring the mixture in a vessel at high speed at 100 °C or higher. - Phenol: 10% by mass - Formaldehyde solution: 6% by mass (40% formaldehyde by mass, 10% methanol by mass, 50% water by mass) - Magnetite 1, treated with the above silane compound: 58 wt% - Magnetite 2, treated with the above silane compound: 26 wt%

[0158] One hundred parts of the above materials, five parts of a 28 wt% ammonia solution, and twenty parts of water were placed in a flask. The temperature was increased to 85 °C over 30 minutes with stirring and mixing and held for three hours to allow a polymerization reaction and harden the resulting phenolic resin. After the hardened phenolic resin had cooled to 30 °C, water was added to the resin and the supernatant was removed. The sediment was rinsed with water and air-dried. The resulting substance was then dried at 60 °C under reduced pressure (5 mmHg or less) to obtain a spherical magnetic support 1 containing dispersed magnetic material. The volume-averaged media particle diameter (D50) was 34.21 µm. Manufacturing example of the two-component developer 1

[0159] The two-component developer 1 was produced by mixing 92.0 parts of the magnetic carrier 1 and 8.0 parts of the toner 1 using a V-mixer (V-20, manufactured by Seishin Enterprise). Production examples of two-component developers 2 to 32.

[0160] Two-component developers 2 to 32 were manufactured in the same way as in the production example of two-component developer 1, except that the specifications were modified as shown in Table 5. Evaluation

[0161] A Canon imagePRESS C10010VP digital printer for commercial printing was modified to allow adjustment of the fusing temperature, processing speed, and DC voltage. DC of the developer bearing element, the charging voltage V DThe electrostatic latent image storage element and the laser power could be freely adjusted. A two-component developer was placed in the black development unit, and images were formed to investigate various properties while a durability test was performed. The results are shown in Table 5. Evaluation of the hot offset resistance - Paper sheet: CS-064 (A4 size, 64.0 g / m²) 2 Base weight) (available from Canon Marketing Japan Inc.) - Amount of toner on paper: 0.08 mg / cm² 2 (adjusted by the DC voltage V) DC of the developer bearing element, the charging voltage V D of the electrostatic latent image bearing element and the laser power) - Image for evaluation: A 2 cm × 20 cm image was placed along the long edge in the feed direction of the A4 sheet of paper, leaving a 2 mm margin from the front edge of the paper. - Test environment: Normal temperature and normal humidity (23 °C temperature, 50% RH humidity (hereafter referred to as N / N)) - Fixing temperature: increased in 5 °C increments from 135 °C - Process speed: 705 mm / s

[0162] The evaluation image described above was output, and the highest fixing temperature at which no hot offset occurred was identified. The hot offset resistance was then evaluated based on this highest fixing temperature according to the following criteria. A rating from AA to C indicated good hot offset resistance.

[0163] Criteria: AA: 170 °C or higher A: 160 °C or higher and lower than 170 °C B: 150 °C or higher and lower than 160 °C C: 140 °C or higher and lower than 150 °C D: lower than 140 °C

[0164] Evaluation of the release agent accumulation on the cleaning blade and the image after the high-speed printing durability test - Amount of toner on paper: Equivalent to 0.08 mg / cm² 2 (adjusted by the DC voltage V) DC of the developer bearing element, the charging voltage V D of the electrostatic latent image bearing element and the laser power) - Image to be printed: A 20 cm × 28 cm image was placed along the long edge in the feed direction of the A4 sheet of paper, leaving a 5 mm wide margin from the front edge and a 5 mm wide margin from the side edges of the sheet of paper. - Test environment: Normal temperature and normal humidity (N / N) - Process speed: 705 mm / s

[0165] The DC voltage V of the aforementioned commercial printer was used. DC of the developer bearing element, the charging voltage V Dof the electrostatic latent image bearing element and the laser power were set in the same way as in the evaluation of the hot offset resistance.

[0166] The toner, primarily transferred to the intermediate transfer belt, was collected with the intermediate transfer belt cleaner without secondary transfer to the paper sheet. The printer described above was subjected to a durability test equivalent to printing on 300,000 sheets of A4 paper. Subsequently, the image described above was printed on CS-064 (A4 size, 64.0 g / m²) paper for evaluation. 2The toner (base weight) was printed and fixed at 160 °C. After the image was printed, the surface of the cleaning blade was examined under an optical microscope, and the printed image was checked for vertical streaks. Vertical streaks occur when the toner melts and adheres to the surface of the electrostatic latent image storage element. The presence of vertical streaks therefore indicates that the toner has melted and adhered to the surface of the electrostatic latent image storage element. If the rating was AA to C, the test result was considered good. Criteria: AA: Neither accumulation of release agent nor vertical streaks were considered. A: A small amount of release agent accumulated, but no vertical stripes were considered. B: The accumulation of release agent was considered, and fine vertical streaks were observed at the edge of the image. C: The accumulation of release agent was considered, and fine vertical streaks were observed at the edge and in the center of the image. D: The accumulation of release agent was observed, and distinct vertical streaks were seen at the edge of the image and fine vertical streaks in the center of the image. E: The accumulation of release agent was considered, and distinct vertical streaks were observed at the edge and in the middle of the image. Table 5 Two-component developer toner Magnetic carrier Hot-offset resistor Image evaluation after high-speed printing durability test Art Art Art °C Example 1 1 1 1 AA 175 AA Example 2 2 2 1 A 165 AA Example 3 3 3 1 B 155 AA Example 4 4 4 1 AA 170 A Example 5 5 5 1 AA 170 B Example 6 6 6 1 A 160 AA Example 7 7 7 1 B 155 AA Example 8 8 8 1 AA 175 A Example 9 9 9 1 AA 175 B Example 10 10 10 1 A 165 C Example 11 11 11 1 A 160 A Example 12 12 12 1 B 150 AA Example 13 13 13 1 C 145 AA Example 14 14 14 1 AA 175 B Example 15 15 15 1 AA 170 C Example 16 16 16 1 C 140 AA Example 17 17 17 1 AA 170 C Example 18 18 18 1 A 160 B Example 19 19 19 1 C 140 C Example 20 20 20 1 C 140 C Example 21 21 21 1 A 170 C Example 22 22 22 1 C 145 A Example 23 23 23 1 B 155 C Example 24 24 24 1 AA 170 A Example 25 25 25 1 AA 175 B Example 26 26 26 1 A 160 AA Example 27 27 27 1 B 155 AA Comparison example 1 28 28 1 D 135 C Comparison example 2 29 29 1 D 135 C Comparison example 3 30 30 1 D 135 E Comparison example 4 31 31 1 D 135 C Comparison example 5 32 32 1 AA 175 D

[0167] The present disclosure can provide a toner that achieves both excellent hot-offset resistance and a reduction in defective images caused by the accumulation of release agent on the cleaning blade, even in high-speed devices compatible with the POD market. The toner disclosed herein can utilize polyethylene terephthalate recycled from used PET bottles or the like as a toner material. The technologies described in this specification have the potential to contribute to achieving a sustainable society, such as a decarbonized / circular economy.

[0168] The present disclosure can provide a toner that achieves both excellent hot-offset resistance and the reduction of defective images caused by the accumulation of the separating agent on the cleaning blade, even in high-speed devices compatible with the POD market.

[0169] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be interpreted as broadly as possible to include all such modifications and equivalent structures and functions. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2000-172008 [0003, 0006] JP 8-239409 [0005, 0006] JP 2024-27954 [0005, 0006]

Claims

[1] Toner having a glass transition temperature Tg of 70 °C or lower, comprising: Toner particles containing a binder resin and a release agent W, wherein the binder resin, which contains an amorphous resin A, is a polyester with a polyester backbone formed from: (i) a polyethylene terephthalate structural segment; and (ii) at least one structure selected from the group consisting of a unit represented by formula (1), a unit represented by formula (2), a unit represented by formula (3) and a unit represented by formula (4): where in formula (1), R1 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, A1 represents a hydrocarbon group, * represents a binding site of the polyester skeleton, and m represents an integer of 2 or more, where in formula (2), R2 represents an alkyl group with 6 to 16 carbon atoms or an alkenyl group with 6 to 16 carbon atoms, B1 represents a hydrocarbon group, * represents a binding site of the polyester skeleton, and n represents an integer of 2 or more, where in formula (3), Each * represents a binding point of the polyester skeleton, and x represents an integer from 6 to 16, where in formula (4), Each * represents a binding point of the polyester skeleton, and y represents an integer from 6 to 16, the release agent W is an ester wax that satisfies the following relationship (C) with the amorphous resin A: 1.90≤SPA−SPW≤2.85 where SP A (cal / cm 3 ) 0,5 denotes the SP value of the amorphous resin A and SP W (cal / cm3 ) 0,5 denotes the SP value of the release agent W, The amorphous resin A satisfies the following relationship (H): 0.27≤WCH / WEG≤1.06 where W EG (mol-%) denotes the percentage of the number of moles of structures in the amorphous resin A that are derived from ethylene glycol in the polyethylene terephthalate structural portion, relative to the total number of moles of alcohol-derived and carboxylic acid-derived structures that form the polyester backbone, and W CH (mol-%) denotes the percentage of the total number of moles in the amorphous resin A of the unit represented by formula (1), the unit represented by formula (2), the unit represented by formula (3), and the unit represented by formula (4), relative to the total number of moles of the alcohol-derived structures and carboxylic acid-derived structures that form the polyester skeleton. [2] Toner according to claim 1, wherein W EG Relationship (D) is fulfilled: 1.27≤WAY≤24.8 [3] Toner according to claim 1 or 2, wherein W CH Relationship (E) fulfilled: 5.6≤WCH≤14.6 [4] Toner according to any one of claims 1 to 3, wherein the ester wax contains an ester compound represented by formula (5): where in formula (5) R3 and R4 each represent an alkyl group with 14 to 24 carbon atoms. [5] Toner according to any one of claims 1 to 4, wherein the ester wax relationship (F) with W CH fulfilled: 0.21≤WW / WCH≤0.69 where W W The quantity in parts by mass of the ester wax relative to 100 parts by mass of the binder resin in the toner is defined. [6] Toner according to any one of claims 1 to 5, wherein W EG and W CH Fulfill relationship (G): 0.34≤WCH / WEG≤0.66 [7] Toner according to any one of claims 1 to 6, wherein the amorphous resin A comprises the unit represented by formula (1) or the unit represented by formula (2).

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