toner

Abstract

To provide a toner exhibiting excellent low-temperature fixability and scratch resistance.SOLUTION: Provided is a toner having toner particles containing a binder resin. The binder resin A contains an amorphous resin A and a crystalline polyester C. The amorphous resin A is a polyester and has, as a structure forming a polyester backbone, (i) a polyethylene terephthalate structure part and (ii) a unit having a predetermined structure. When an SP value of the amorphous resin A is defined as SPA and an SP value of the crystalline polyester C is defined as SPC, 1.00≤SPA-SPC≤1.35 is satisfied. The toner further contains a phosphorus element derived from a phosphorus compound, and the content of a phosphorus element in the toner, based on the total mass of the toner, is in a range from 5 to 500 ppm.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to toners used in electrophotography, electrostatic recording, electrostatic printing, and the like. [Background technology]

[0002] In recent years, as electrophotographic full-color copiers have become more widespread, there is a demand for not only higher speeds and higher image quality, but also additional performance improvements such as energy-saving performance to reduce running costs, compatibility with a wide variety of media that can be expanded beyond plain office paper to include bookbinding and package printing, etc. Furthermore, consideration is being given to reducing the environmental impact of the materials used.

[0003] Specifically, toners that can be fixed at lower temperatures and have excellent low-temperature fixing properties are required to reduce power consumption in the fixing process and to meet energy conservation needs. Furthermore, when a thick coated paper used in bookbinding or package printing comes into contact with a human fingernail or a sharp object, the depth of penetration into the media increases, increasing the contact area. This can cause the toner to peel off from the media due to strong external stress, resulting in image defects. This can lead to a phenomenon known as "scratching." Therefore, toners with excellent scratch resistance that can withstand external stresses on thick coated paper are required.

[0004] Therefore, Patent Document 1 proposes a toner using a crystalline resin as a toner with excellent low-temperature fixing properties, and Patent Document 2 proposes a toner containing inorganic fine particles with a high dielectric constant as a toner with excellent scratch resistance.

[0005] Meanwhile, in recent years, the reuse and effective utilization of used PET bottles and other plastic products has become a major issue, including environmental and resource issues. As the number of PET bottles sold increases, there is a demand for improved recycling rates. PET bottles can be recycled using them for sheet applications such as food trays, for fiber applications such as clothing, and by using bottle-to-bottle horizontal recycling. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-156074 [Patent Document 2] Japanese Patent Publication No. 2020-34647 Summary of the Invention [Problem to be solved by the invention]

[0007] The toner described in Patent Document 1 has a sharp melting property and therefore exhibits excellent low-temperature fixability.

[0008] Furthermore, Patent Document 2 proposes a technology for improving scratch resistance by changing inorganic fine particles that exist at the interfaces of toner particles in a printed image and cause deterioration of scratch resistance to inorganic fine particles with a high dielectric constant.

[0009] However, with a toner having excellent low-temperature fixability as described in Patent Document 1, scratches may occur in printed images due to fracture of the toner particles themselves, rather than at the toner particle interfaces. Therefore, even when the technology described in Patent Document 2 is applied, scratches may still occur.

[0010] As described above, there is room for improvement in achieving both low-temperature fixability and scratch resistance. Therefore, there is an urgent need to develop a toner that exhibits excellent low-temperature fixability and scratch resistance. The present disclosure provides a toner that exhibits excellent low-temperature fixability and scratch resistance. [Means for solving the problem]

[0011] The present disclosure provides a toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The amorphous resin A is a polyester, and the structure forming the polyester skeleton is (i) a polyethylene terephthalate structure, and (ii) at least one structure selected from the group consisting of a unit represented by the following formula (1), a unit represented by the following formula (2), a unit represented by the following formula (3), and a unit represented by the following formula (4): and

[0012] [ka]

[0013] (In formula (1), R1 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A1 represents a hydrocarbon group; * represents a bond in the polyester backbone, m represents an integer of 2 or greater.

[0014] [ka]

[0015] (In formula (2), R2 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B1 represents a hydrocarbon group; * represents a bond in the polyester backbone, n represents an integer of 2 or greater.

[0016] [ka]

[0017] (In formula (3), * represents a bond in the polyester skeleton, x represents an integer of 6 to 16.

[0018] [ka]

[0019] (In formula (4), * represents a bond in the polyester skeleton, y represents an integer from 6 to 16.

[0020] The SP value of the amorphous resin A is A (cal / cm 3 ) 0.5 The SP value of the crystalline polyester C is SP C (cal / cm 3 ) 0.5 When this is done, the SP A and the SP C and satisfy the following formula (C), 1.00≦SP A -SP C ≦1.35 (C) the toner contains a phosphorus element derived from a phosphorus compound, The content of the phosphorus element in the toner based on the mass of the toner is W P (ppm), the W P The toner satisfies the following formula (D): 5≦W P ≦500 (D) [Effects of the Invention]

[0021] According to the present disclosure, it is possible to provide a toner that exhibits excellent low-temperature fixability and scratch resistance. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present disclosure will be described in detail below, but is not limited to these descriptions. In this disclosure, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, a monomer unit refers to a structure formed by the reaction of a monomer in a polymer. Furthermore, a crystalline polyester is a polyester that shows a clear endothermic peak in differential scanning calorimetry (DSC).

[0023] The present inventors have conducted research into toners that are excellent in low-temperature fixability and scratch resistance.

[0024] The present inventors first investigated the possibility of improving scratch resistance by increasing the Young's modulus of the toner. Specifically, by adjusting the molecular weight of the binder resin to a certain level or by selecting an aromatic monomer as a component, a certain degree of effect on scratch resistance was achieved. However, it was found that this resulted in an increase in the glass transition temperature and softening point of the toner, impairing low-temperature fixability.

[0025] In other words, it has become clear that it is difficult to achieve both low-temperature fixability and scratch resistance simply by controlling the Young's modulus of the toner.

[0026] Therefore, instead of suppressing deformation by increasing the Young's modulus, the present inventors have investigated the possibility of imparting toner with "elastic deformation characteristics" that will cause temporary deformation in response to an external force but restore the original shape when the external force is released. In other words, the inventors have investigated the possibility of developing a toner that exhibits good low-temperature fixability and also has the following characteristics: (i) The three-dimensional structure can be flexibly deformed in the direction of the applied external force. (ii) When the external force is removed, it can return to its original conformation.

[0027] Such a toner can be achieved by using the following composition.

[0028] That is, the toner of the present disclosure is a toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The amorphous resin A is a polyester, and the structure forming the polyester skeleton is (i) a polyethylene terephthalate structure, and (ii) at least one structure (hereinafter also referred to as "unit") selected from the group consisting of a unit represented by the following formula (1), a unit represented by the following formula (2), a unit represented by the following formula (3), and a unit represented by the following formula (4), and

[0029] [ka]

[0030] (In formula (1), R1 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A1 represents a hydrocarbon group; * represents a bond in the polyester backbone, m represents an integer of 2 or greater.

[0031] [ka]

[0032] (In formula (2), R2 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B1 represents a hydrocarbon group; * represents a bond in the polyester backbone, n represents an integer of 2 or greater.

[0033] [ka]

[0034] (In formula (3), * represents a bond in the polyester skeleton, x represents an integer of 6 to 16.

[0035] [ka]

[0036] (In formula (4), * represents a bond in the polyester skeleton, y represents an integer from 6 to 16.

[0037] The SP value of the amorphous resin A is A (cal / cm 3 ) 0.5 The SP value of the crystalline polyester C is SP C (cal / cm 3 ) 0.5 When this is done, the SP A and the SP C and satisfy the following formula (C), 1.00≦SP A -SP C ≦1.35 (C) the toner contains a phosphorus element derived from a phosphorus compound, The content of the phosphorus element in the toner based on the mass of the toner is W P (ppm), the W P is characterized in that the following formula (D) is satisfied. 5≦W P ≦500 (D)

[0038] The mechanism by which both low-temperature fixability and scratch resistance are achieved is presumed to be as follows.

[0039] The amorphous resin A has 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). The SP value between the amorphous resin A and the crystalline polyester C is controlled. This gives the amorphous resin A affinity with the crystalline polyester C. Therefore, in a fixed image, the amorphous resin A is influenced by the crystalline polyester C and becomes flexible. This structure disperses applied external forces, allowing the three-dimensional structure to flexibly deform in the direction of the applied external force without breaking the molecular chain. Furthermore, the amorphous resin A contains a polyethylene terephthalate structural unit, and therefore has a repeating structure of a condensate of terephthalic acid and ethylene glycol in the polyester skeleton. The ethylene glycol-derived structure of the polyethylene terephthalate structural unit has ester groups at a very close molecular distance of two carbon atoms due to esterification at both ends of the ethylene glycol. Therefore, the amorphous resin A has ester groups localized within the resin. Furthermore, the phosphorus compound to which the three unshared electron pairs in the outermost shell have reacted also has a bonding point at a very close molecular distance. Therefore, the amorphous resin A can interact with the localized ester groups in the amorphous resin A, centering on the phosphorus element of the phosphorus compound, to form a three-dimensional crosslinked structure. This structure allows the resin to return to its original three-dimensional structure from a deformed state when the applied external force is removed. As described above, it is believed that the configuration of the present disclosure can provide excellent low-temperature fixability and scratch resistance.

[0040] The amorphous resin A of the present disclosure has 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) as a structure forming a polyester skeleton. The structures of long-chain hydrocarbon groups, such as alkyl groups and alkenyl groups, contained in the units represented by formula (1), (2), (3), and (4) are relatively less polar than the ethylene glycol-derived structure of the polyethylene terephthalate structural portion. Therefore, the structures of long-chain hydrocarbon groups, such as alkyl groups and alkenyl groups, contained in the units represented by formula (1), (2), (3), and (4) are more flexible due to their increased affinity with the crystalline polyester C. This structure disperses applied external forces, allowing the three-dimensional structure to flexibly deform in the direction of the applied external force without breaking the molecular chain. As a result, improved elastic deformation is achieved, resulting in excellent scratch resistance. Furthermore, the SP of the amorphous resin A of the present disclosure A (cal / cm 3 ) 0.5 and crystalline polyester C SP C (cal / cm 3 ) 0.5 satisfies the above formula (C). SP A -SP C When formula (C) is satisfied, the amorphous resin A and the crystalline polyester C are easily compatible with each other, allowing the crystalline polyester C to smoothly interact with the structure of the amorphous resin A containing long-chain hydrocarbon groups, such as alkyl or alkenyl groups. This structure therefore becomes flexible due to its increased affinity with the crystalline polyester C. Furthermore, this structure disperses applied external forces, allowing the three-dimensional structure to flexibly deform in the direction of the applied external force without breaking the molecular chains. As a result, improved elastic deformation properties are achieved, resulting in excellent scratch resistance.

[0041] Furthermore, the toner of the present disclosure contains a phosphorus element derived from a phosphorus compound, and W P(ppm) satisfies the above formula (D). When the content of phosphorus in the toner satisfies the above formula (D), it indicates that there is a sufficient amount of phosphorus to form a three-dimensional crosslinked structure by interacting with the localized ester groups in the amorphous resin A, with the phosphorus at the center. In other words, it is the minimum amount of phosphorus that can flexibly change the three-dimensional structure in the direction of the applied external force without breaking the molecular chain in order to disperse the applied external force, and the maximum amount of phosphorus that can ensure a certain level of plastic deformation that ensures low-temperature fixability.

[0042] The toner of the present disclosure EG It is preferable that W (mol %) satisfies the following formula (E) from the viewpoint of excellent low-temperature fixability and scratch resistance. EG (mol %) is the ratio of the structure derived from ethylene glycol in the polyethylene terephthalate structure to the total number of moles of the structure derived from alcohol and the structure derived from carboxylic acid that form the polyester skeleton in the amorphous resin A. EG In calculating the molar percentage (mol %), the polyethylene terephthalate portion is decomposed into units derived from ethylene glycol and units derived from terephthalic acid, and the number of moles is handled. 12.6≦W EG ≦24.8 (E)

[0043] W EG When the W content is 12.6 mol % or more, the applied external force is dispersed, so that the molecular chains are not broken and the three-dimensional structure can be more flexibly deformed in the direction of the applied external force, thereby improving scratch resistance. EG When the content is 24.8 mol % or less, a certain level of plastic deformation that can ensure low-temperature fixability can be ensured.

[0044] The toner of the present disclosure CH It is preferable that W (mol %) satisfies the following formula (F) from the viewpoint of excellent low-temperature fixability and scratch resistance. CH(mol %) is the total ratio 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) to the total number of moles of the alcohol-derived structures and the carboxylic acid-derived structures that form the polyester skeleton in the amorphous resin A. In addition, W CH In calculating the molar percentage (mol %), the polyethylene terephthalate portion is decomposed into units derived from ethylene glycol and units derived from terephthalic acid, and the number of moles is handled. 5.6≦W CH ≦14.6 (F)

[0045] W CH When the W content is 5.6 mol % or more, the affinity between the long-chain hydrocarbon groups such as alkyl groups and alkenyl groups in the amorphous resin A and the crystalline polyester C is enhanced, and the resin can return to its original three-dimensional structure when the applied external force is removed. As a result, scratch resistance is improved. CH When the content is 14.6 mol % or less, the applied external force is dispersed, so that the molecular chains are not broken and the three-dimensional structure can be flexibly changed in the direction of the applied external force, thereby improving scratch resistance.

[0046] The crystalline polyester C of the present disclosure is preferably a modified crystalline polyester having a structure in which the hydroxy group at the terminal of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or a modified crystalline polyester having a structure in which the carboxy group at the terminal of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms. When the crystalline polyester C is the above-mentioned modified crystalline polyester, the structure of the long-chain hydrocarbon group, such as an alkyl group or alkenyl group, of the amorphous resin A is sufficiently longer, thereby promoting flexibility. Furthermore, this structure disperses applied external forces, allowing the three-dimensional structure to flexibly deform in the direction of the applied external force without breaking the molecular chain, thereby achieving excellent scratch resistance.

[0047] The toner of the present disclosure CH (mol%) and W EGFrom the viewpoint of excellent scratch resistance, it is preferable that (mol %) satisfies the following formula (G): 0.42≦W CH / W EG ≦0.68 (G)

[0048] W CH / W EG If W is 0.42 or more, the molecule can return to its original three-dimensional structure when the applied external force is removed. CH / W EG When the value is 0.68 or less, the applied external force is dispersed, and the molecular chains are not broken, and the three-dimensional structure can be flexibly changed in the direction of the applied external force.

[0049] The toner of the present disclosure EG (mol%) and W P From the viewpoint of excellent scratch resistance, it is preferable that (ppm) satisfies the following formula (H): 0.05≦W EG / W P ≦0.11 (H)

[0050] W EG / W P When W is 0.05 (mol % / ppm) or more, a certain level of plastic deformation that can ensure low-temperature fixability can be ensured. EG / W P When the mol % / ppm is 0.11 or less, the molecule can return to its original three-dimensional structure when the applied external force is removed.

[0051] The ratio of the content (parts by mass) of crystalline polyester C to 100 parts by mass of the binder resin of the toner of the present disclosure is W C (mass%), W C and W CH It is preferable that the toner satisfies the following formula (I) from the viewpoint of low-temperature fixability and scratch resistance. 40.0≦W CH / W C ≦145.0 (I)

[0052] W CH / W CWhen the W is 40.0 (mol % / mass %) or more, the applied external force is dispersed, and the molecular chains are not broken, and the three-dimensional structure can be flexibly deformed in the direction of the applied external force. CH / W C When the ratio is 145.0 (mol % / mass %) or less, a certain level of plastic deformation that can ensure low-temperature fixability can be ensured.

[0053] <Amorphous resin A> The amorphous resin A is a polyester and has the following (i) and (ii) as structures forming the polyester skeleton. (i) Polyethylene terephthalate structural part (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);

[0054] The polyethylene terephthalate structure used in the amorphous resin A is obtained by polycondensing ethylene glycol and terephthalic acid.

[0055] The polyester synthesis can be carried out in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification promoter, a polymerization inhibitor, etc., at a temperature preferably of 180°C or higher and 250°C or lower.

[0056] Examples of esterification catalysts include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamine. Among these, tin compounds such as tin(II) 2-ethylhexanoate are preferred. The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less, per 100 parts by mass of the raw material monomers (alcohol component, carboxylic acid component, and PET). Examples of esterification promoters include gallic acid. The amount of the esterification promoter used is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 0.5 parts by mass or less, more preferably 0.1 parts by mass or less, per 100 parts by mass of the raw material monomers. Examples of polymerization inhibitors include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less, per 100 parts by mass of the raw material monomer.

[0057] In addition, in the synthesis of polyester, polyethylene terephthalate may be present from the start of the polycondensation reaction, or may be added to the reaction system during the polycondensation reaction. In order for the polyethylene terephthalate structural part to be incorporated into the main skeleton of the polyester in a block form to some extent, the timing of adding polyethylene terephthalate is preferably when the reaction rate between the alcohol component and the carboxylic acid component is 10% or less, more preferably 5% or less. Here, the reaction rate means Amount of water produced by reaction (mol) / Amount of water produced when all components react (mol) × 100 This refers to the value of

[0058] The polyethylene terephthalate structural unit contained in the amorphous resin A preferably has a repeating structure of a condensate of terephthalic acid and EG, as represented by the following formula (5): In formula (5), p is preferably 3 or more and 10 or less, and more preferably 4 or more and 8 or less. When p is in this range, the EG-derived structure contained in the polyethylene terephthalate structural unit contained in the amorphous resin A is more suitably localized, and the interaction between the localized EG-derived structure and the phosphorus element improves scratch resistance.

[0059] [ka]

[0060] (In formula (5), * represents a bond in the polyester skeleton, p represents an integer of 3 to 10.

[0061] Furthermore, used polyethylene terephthalate (so-called recycled PET) can be used as the polyethylene terephthalate structural portion contained in the amorphous resin A. Reusing polyethylene terephthalate is preferable from an environmental perspective.

[0062] Used PET is collected, washed, sorted to remove other materials and waste, and then crushed into flakes or other shapes. The crushed material can be used as is, or it can be kneaded and coarsely crushed before use. If conventional cleaning is unable to sufficiently remove chemicals adsorbed to the surface of PET bottles, alkaline cleaning can be performed. If the crushed material is partially hydrolyzed by alkaline cleaning, it is preferable to melt the washed crushed material and pelletize it to restore the reduced degree of polymerization. The solid-state polymerization process can be carried out by continuous solid-state polymerization of washed flakes or pellets made by melt-extrusion of flakes in an inert gas such as nitrogen gas or a rare gas at 180-245°C, preferably 200-240°C. Alternatively, the washed crushed material can be depolymerized to break down into monomer units and resynthesized. The recycled PET is not limited to the above-mentioned used PET; off-spec PET fiber waste or pellets discharged from factories can also be used.

[0063] Furthermore, in order to incorporate at least one unit 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) into the amorphous resin A, the following monomers can be used: 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, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dodecenylsuccinic acid, n-octylsuccinic acid, isododecenylsuccinic acid, dodecylsuccinic acid, isooctenylsuccinic acid, hexadecylsuccinic acid, and the like.

[0064] Among the units represented by formula (1), (2), (3), and (4), the units represented by formula (1) and (2) are preferred. The alkyl or alkenyl group having 6 to 16 carbon atoms branched from the main chain of the polyester skeleton increases the affinity with the release agent, further improving the dispersibility of the release agent.

[0065] In addition, in addition to the above-described structures and monomers, other polyhydric alcohols (divalent or higher alcohols), polycarboxylic acids (divalent or higher carboxylic acids), acid anhydrides thereof, or lower alkyl esters thereof may also be used as components for obtaining amorphous resin A.

[0066] The following polyhydric alcohol monomers can be used as the polyhydric alcohol monomer: Dihydric alcohol components include ethylene glycol, propylene 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 bisphenols represented by formula (A) and their derivatives;

[0067] [ka]

[0068] (In formula (A), R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)

[0069] Diols represented by formula (B);

[0070] [ka]

[0071] (In formula (B), R' represents -CH2-CH2-, -CH2-CH(-CH3)-, or -CH2-C(-CH3)2-, x' and y' are integers of 0 or more, and the average value of x'+y' is 0 to 10.)

[0072] Examples include:

[0073] Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferred.

[0074] These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

[0075] Examples of dicarboxylic acid components include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, azelaic acid, malonic acid, anhydrides of these acids, and lower alkyl esters of these acids. Of these, maleic acid, fumaric acid, and terephthalic acid are preferably used.

[0076] Examples of trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include 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-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, and their acid anhydrides or lower alkyl esters. Among these, 1,2,4-benzenetricarboxylic acid, i.e., trimellitic acid or its derivatives, is particularly preferred due to its low cost and easy reaction control. These divalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination.

[0077] The method for producing the amorphous resin A is not particularly limited, and known methods can be used. For example, the aforementioned alcohol monomer and carboxylic acid monomer are simultaneously charged and polymerized via an esterification reaction or transesterification reaction and a condensation reaction to produce a polyester. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization of the polyester unit can be performed using polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide. In particular, the amorphous resin A is preferably a polyester polymerized using a tin-based catalyst.

[0078] The amorphous resin A may be a polyester having a vinyl resin portion. A preferred method for obtaining a polyester having a vinyl resin bonded thereto is to use a monomer component capable of reacting with both the vinyl resin and the polyester unit. Such a monomer is preferably a monomer having an unsaturated double bond and a carboxyl group or a hydroxyl group. Examples of such a monomer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or their anhydrides, and acrylic acid or methacrylic acid esters.

[0079] The peak molecular weight of the amorphous resin A is preferably 3500 or more and 20000 or less from the viewpoint of low-temperature fixability, etc. The glass transition temperature is preferably 40°C to 70°C.

[0080] Furthermore, as the amorphous resin, various resins conventionally known as binder resins can be used in combination with the amorphous resin A. Examples of such resins include phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.

[0081] <Crystalline Polyester C> Monomers used in the polyester unit of the crystalline polyester C used in the toner of the present disclosure include polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric or higher carboxylic acids), their acid anhydrides or their lower alkyl esters.

[0082] As the polyhydric alcohol monomer used in the polyester unit of the crystalline polyester C, the following polyhydric alcohol monomers can be used.

[0083] The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably a straight-chain) aliphatic diol, 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. Among these, particularly preferred are straight-chain aliphatic α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol.

[0084] In the present disclosure, polyhydric alcohol monomers other than the above polyhydric alcohols can also be used. Among the polyhydric alcohol monomers, dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol; and the like. Furthermore, among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0085] As the polycarboxylic acid monomer used in the polyester unit of the crystalline polyester C, the following polycarboxylic acid monomers can be used.

[0086] The polycarboxylic acid monomer is not particularly limited, but is preferably a chain (more preferably a linear) aliphatic dicarboxylic acid. Specific 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, and itaconic acid, as well as those obtained by hydrolyzing the acid anhydrides or lower alkyl esters of these acids.

[0087] In the present disclosure, polycarboxylic acids other than the above-mentioned polycarboxylic acid monomers can also be used. Among the other polycarboxylic acid monomers, dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, as well as their acid anhydrides and lower alkyl esters. Furthermore, among the other carboxylic acid monomers, tricarboxylic or higher polycarboxylic 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; and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, as well as their acid anhydrides and lower alkyl esters.

[0088] Furthermore, the crystalline polyester C is preferably a modified crystalline polyester having a structure in which the hydroxy group at the end of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or a modified crystalline polyester having a structure in which the carboxy group at the end of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms.

[0089] Examples of aliphatic monocarboxylic acid monomers having 16 to 31 carbon atoms include palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (icosanoic acid), henicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic acid.

[0090] Examples of aliphatic monoalcohols having 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 myricyl alcohol.

[0091] Crystalline polyester C can be produced by a conventional polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are subjected to an esterification reaction or a transesterification reaction, followed by a conventional polycondensation reaction under reduced pressure or by introducing nitrogen gas to obtain a crystalline polyester. Then, the aliphatic compound is added and the esterification reaction is carried out to obtain the desired crystalline polyester.

[0092] The above esterification or transesterification reaction can be carried out, if necessary, using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate.

[0093] The polycondensation reaction can be carried out using a conventional polymerization catalyst, such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. The polymerization temperature and the amount of catalyst are not particularly limited and may be determined appropriately.

[0094] In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be charged at once to increase the strength of the resulting crystalline polyester. Alternatively, to reduce the amount of low-molecular-weight components, a divalent monomer may be reacted first, and then a trivalent or higher valent monomer may be added and reacted.

[0095] From the viewpoint of low-temperature fixability, the melting point of the crystalline polyester C is preferably 70° C. to 110° C., more preferably 80° C. to 100° C. In the toner of the present disclosure, the crystalline polyester C is preferably used in an amount of 3 parts by mass to 20 parts by mass per 100 parts by mass of the amorphous resin, from the viewpoints of low-temperature fixability, scratch resistance, and charge retention in a high-temperature, high-humidity environment.

[0096] <Phosphorus compounds> Examples of phosphorus compounds that can be used in the toner of the present disclosure include trisodium phosphate, trimethyl phosphate, triethyl phosphate, tri-2-ethylhexyl phosphate, (trisisopropylphenyl) phosphate, triphenyl phosphate, tributyl phosphate, trimethyl phosphite, tributyl phosphite, triphenyl phosphite, etc. Among these, trivalent phosphorus compounds that can easily form three-dimensional crosslinks are preferred.

[0097] The phosphorus content and the optimum W content for forming a three-dimensional cross-linked structure EG and W P As described above, in order to form a three-dimensional crosslinked structure, it is necessary to use used polyethylene terephthalate (so-called recycled PET), as this makes it easier for polyethylene terephthalate blocks to form, allowing ester groups with close molecular distances to gather together more effectively, forming a strong three-dimensional crosslinked structure. This structure can return to its original three-dimensional structure when the applied external force is removed.

[0098] <Wax> The toner particles may contain wax. Examples of wax include the following.

[0099] Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene Saturated fatty acid bisamides such as bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0100] Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferred from the viewpoint of suppressing blooming. That is, the wax preferably contains a hydrocarbon wax. More preferably, the wax is Fischer-Tropsch wax.

[0101] From the viewpoint of suppressing blooming, the content of the wax is preferably 2 to 10 parts by mass, more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the binder resin.

[0102] The melting point of the wax is preferably 60°C or higher and 120°C or lower, and more preferably 90°C or higher and 110°C or lower.

[0103] <Coloring agent> The toner particles may contain a colorant as needed. Examples of colorants include the following: Black colorants include carbon black; and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination. From the viewpoint of the image quality of full-color images, it is preferable to use a dye and a pigment in combination.

[0104] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0105] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0106] Examples of 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 pigments in which one to five phthalimidomethyl groups are substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0107] Examples of yellow toner pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, and 185; and CI Vat Yellow 1, 3, and 20. CI Pigment Yellow 180 may be treated with 1 to 10% by weight of a nonionic surfactant (such as polyoxyethylene alkyl ether). Examples of yellow toner dyes include CI Solvent Yellow 162.

[0108] These colorants may be used alone or in combination, or in the form of a solid solution. The colorant is selected in consideration of hue angle, chroma, brightness, lightfastness, transparency on an overhead projector (OHP), and dispersibility in toner particles.

[0109] The content of the colorant is preferably 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0110] <Charge control agent> The toner particles may contain a charge control agent as needed. By incorporating a charge control agent, the charging characteristics can be stabilized, and the optimal triboelectric charge amount can be controlled according to the development system. As the charge control agent, known substances can be used, but in particular, metal compounds of aromatic carboxylic acids are preferred because they are colorless, have a high charging speed of the toner, and can stably maintain a constant charge amount.

[0111] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0112] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the binder resin.

[0113] <Inorganic fine particles> The toner may contain inorganic fine particles as needed.

[0114] The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. Examples of the inorganic fine particles include silica fine particles, titanium oxide fine particles, alumina fine particles, and fine particles of their double oxides. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0115] <External additives> As the external additive, in addition to the inorganic fine particles described above, organic fine particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles may be used.

[0116] From the viewpoint of improving flowability, the median diameter (D50) of the external additives on a number basis is preferably 10 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 90 nm or less.

[0117] The content of the external additive is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0118] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it is preferable to use the toner as a two-component developer by mixing it with a magnetic carrier.

[0119] Examples of magnetic carriers that can be used include generally known ones such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state.

[0120] When the toner is mixed with a magnetic carrier and used as a two-component developer, the toner concentration in the two-component developer is preferably 2% by mass to 15% by mass, and more preferably 4% by mass to 13% by mass.

[0121] <Method of manufacturing toner particles> The method for producing toner particles is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used. Among these, the pulverization method is preferred from the viewpoint of controlling the wax on the surface of the toner particles. In other words, the toner particles are preferably pulverized toner particles. The procedure for producing toner using the pulverization method will be described below.

[0122] The pulverization method includes, for example, a raw material mixing step of mixing a crystalline polyester C and an amorphous resin A as binder resins, a phosphorus compound, and, if necessary, other components such as other amorphous resins, waxes, colorants, and charge control agents; a step of melting and kneading the mixed raw materials to obtain a resin composition; and a step of pulverizing the obtained resin composition to obtain toner particles.

[0123] In the raw material mixing process, materials constituting the toner particles, such as binder resin, wax, and, if necessary, other components such as colorants and charge control agents, are weighed out in predetermined amounts, blended, and mixed. Examples of mixing devices include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0124] Next, the mixed materials are melt-kneaded to disperse the materials in the binder resin. In this melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Single- or twin-screw extruders are the mainstream due to their advantage of continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Ko-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled using a twin roll or the like and cooled with water or the like in a cooling process.

[0125] The cooled resin composition is then pulverized to the desired particle size in a pulverization process. In the pulverization process, the resin composition is first coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill. The pulverized resin composition is then finely pulverized using a pulverizer such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet pulverizer.

[0126] Thereafter, as necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation).

[0127] Subsequently, if necessary, external additives such as silica fine particles are added to the surface of the toner particles to obtain the toner. Examples of equipment for external addition include a double cone mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), and Nobilta (manufactured by Hosokawa Micron Corporation).

[0128] Before or after the external addition treatment, the toner particles may be subjected to hot air treatment as needed to make them spherical.

[0129] The methods for measuring various physical properties are explained below.

[0130] (Method of separating each material from toner) By utilizing the difference in solubility of each material in the toner in a solvent and GPC, each material can be separated from the toner. The following physical properties can be measured using each separated material.

[0131] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble components (amorphous resin A, amorphous resin B, crystalline polyester C, phosphorus compounds) are separated from the insoluble components (wax, colorants, inorganic particles, etc.).

[0132] Second separation: The soluble fraction (amorphous resin A, amorphous resin B, crystalline polyester C, phosphorus compound) obtained in the first separation is dissolved in tetrahydrofuran (THF) at 23°C, and the soluble fraction (amorphous resin A, amorphous resin B, phosphorus compound) and the insoluble fraction (crystalline polyester C) are separated.

[0133] Third separation: The insoluble matter (wax, colorant, inorganic fine particles, etc.) obtained in the first separation is dissolved in MEK at 100°C, and the soluble matter (wax) is separated from the insoluble matter (colorant, inorganic fine particles, etc.).

[0134] Fourth separation: The soluble fractions (amorphous resin A, amorphous resin B, and phosphorus compounds) obtained in the second separation are dissolved in tetrahydrofuran (THF) at 23°C, and the amorphous resin A, amorphous resin B, and phosphorus compounds are separated by preparative GPC.

[0135] <Method for identifying and measuring the content of various monomer units in amorphous resins and crystalline polyesters> Confirmation of the identity of various monomer units in amorphous resin and crystalline polyester and measurement of their content ratios are 1 H-NMR was performed under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Accumulation count: 64 times Measurement temperature: 30℃ Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl3) is added as a solvent, and the sample is dissolved in a thermostatic bath at 40°C.

[0136] obtained 1 The structure of each monomer unit is identified from the H-NMR chart, and the integral value S of the peaks assigned to each monomer unit is calculated. 1、 S 2、 S3, S n Calculate.

[0137] The content ratio of each monomer unit is determined by the above integral values ​​S1, S2, S3 and S n It is calculated as follows using the following: 2、 n3···n n is the number of hydrogens in each monomer unit. Content ratio of various monomer units (mol%) = {(S n / n n ) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S n / n n ))}×100

[0138] The content ratio (mol%) of each monomer unit is calculated by changing the molecular term in the same operation. Note that when a polymerizable monomer that does not contain a hydrogen atom is used in each monomer unit, 13 Measured nuclei using C-NMR 13 C, and measurements were taken in single pulse mode. 1 Calculate in the same manner by H-NMR.

[0139] <Method for calculating the SP value of amorphous resin and crystalline polyester> The SP values ​​of the amorphous resin and the crystalline polyester are calculated according to the calculation method proposed by Fedors.

[0140] Specifically, the evaporation energy (Δei), molar volume (Δvi), and molar ratio (j) in the resin of each monomer unit are determined, and the SP value is calculated using the following formula. SP value (cal / cm 3 ) 0.5 ={(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5

[0141] The evaporation energy (Δei) and molar volume (Δvi) of the atom or atomic group in the monomer unit are the values ​​described in "Polym. Eng. Sci., 14(2), 147-154 (1974)".

[0142] <Content of phosphorus element in toner WP Measurement method Content W of phosphorus element in toner P (ppm) is measured using a multi-element simultaneous ICP emission spectrometer Vista-PRO (manufactured by Hitachi High-Tech Science Corporation).[[ID=...]]After passing the decomposition solution through filter paper (5C), transfer it to a 50 mL volumetric flask and make up to 50 mL with ultrapure water. By measuring the aqueous solution in the volumetric flask with a multi-element simultaneous ICP emission spectrometer Vista-PRO under the following conditions, the content of phosphorus element in the toner can be quantified. The quantification of the content is calculated based on the calibration curve prepared using a standard sample of the element to be quantified. Conditions: RF power 1.20 kW, Ar gas: Plasma flow 15.0 L / min, Auxiliary flow: 1.50 L / min, MFC: 1.50 L / min, Nebulizer flow: 0.90 L / min, Liquid delivery pump speed: 15 rpm, Measurement repetition: 3 times, Measurement time: 1.0 s

[0145] <000......]]<Measurement method of weight average molecular weight Mw of amorphous resin by GPC> The molecular weight (Mw) of the THF-soluble component of the amorphous resin is measured by gel permeation chromatography (GPC) as follows. [[ID=4...]] ​​​​​​​​​​​First, dissolve the toner in tetrahydrofuran (THF) at room temperature over 24 hours. Then, filter the resulting solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is about 0.8% by mass. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko K.K.) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Oven temperature: 40.0 °C Sample injection volume: 0.10 mL

[0147] When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0148] <Method for Measuring the Weight-Average Molecular Weight of Crystalline Polyester by GPC> The weight-average molecular weight (Mw) of the toluene-soluble component of the crystalline polyester at 100 °C is measured by gel permeation chromatography (GPC) as follows.

[0149] First, dissolve the crystalline polyester in toluene at 100 °C over 1 hour. Then, filter the resulting solution through a solvent-resistant membrane filter "Maechori Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in toluene is about 0.1% by mass. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT (7.8 cm ID x 30 cm) in duplicate (Tosoh Corporation) Detector: High temperature RI Temperature: 135℃ Solvent: toluene Flow rate: 1.0mL / min Sample: 0.4 mL of 0.1% sample injected

[0150] The molecular weight of the sample is calculated using a molecular weight calibration curve prepared using monodisperse polystyrene standard samples, and then converted into polyethylene using a conversion formula derived from the Mark-Houwink viscosity formula.

[0151] <Method for measuring the glass transition temperature Tg of amorphous resin> The glass transition temperature Tg of the amorphous resin is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) in accordance with ASTM D3418-82. The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the heat quantity. Specifically, approximately 3 mg of amorphous resin is precisely weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and the measurement is performed under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃

[0152] Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C once and held there for 10 minutes, then lowered to 30°C, and then raised again. During this second heating process, the specific heat change is measured in the temperature range of 30 to 100°C. The intersection of the line midway between the baselines before and after the specific heat change appears and the differential thermal curve is taken as the glass transition temperature Tg of the amorphous resin.

[0153] < Melting peak temperature (melting point) of crystalline polyester, etc. T C (℃) measurement method> Melting point (TC ) is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) in accordance with ASTM D3418-82.

[0154] The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat. Specifically, 3 mg of sample is precisely weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are performed under the following conditions: Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃

[0155] Measurements are performed over a range of 30 to 180°C at a heating rate of 10°C / min. The temperature is first raised to 180°C and held there for 10 minutes, then lowered to 30°C, and then raised again. During this second heating process, the temperature at which the maximum endothermic peak occurs in the temperature-endothermic curve in the range of 30 to 100°C is taken as the melting point. [Example]

[0156] The present disclosure will be described in more detail below using examples and comparative examples, but these are not intended to limit the present disclosure in any way. In the following formulations, parts are by mass unless otherwise specified.

[0157] <Preparation of amorphous resin A1> Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1) :20.9 parts (42.0mol%) Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) :47.4 parts (29.0mol%) 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 (cocatalyst): 0.1 parts

[0158] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. The molar ratio of polyethylene terephthalate is the value of the number of units obtained by adding together the number of units derived from ethylene glycol and the number of units derived from terephthalic acid.

[0159] Next, the inside of the reaction vessel was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the mixture was reacted at 200°C for 2 hours with stirring.

[0160] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the mixture was allowed to react for 5 hours while maintaining the temperature at 200°C. After confirming that the weight-average molecular weight had reached 6700, the temperature was lowered to terminate the reaction, yielding an amorphous resin A1 having a polyethylene terephthalate structural unit in its molecule. The physical properties of the amorphous resin A1 obtained by the above-described measurement methods are shown in Table 1-1.

[0161] <Preparation of Amorphous Resins A2 to A10 and Amorphous Resins A12 to A17> Amorphous resins A2 to A10 and A12 to A17 each having a polyethylene terephthalate structural unit in the molecule were obtained by carrying out the reaction in the same manner as in the preparation of amorphous resin A1, except that the types and amounts of polyethylene terephthalate and polymerizable monomers were changed as shown in Tables 1-1 to 1-3. The physical properties of amorphous resins A2 to A10 and A12 to A17 obtained by the above-mentioned measurement methods are shown in Tables 1-1 to 1-3.

[0162] <Preparation of amorphous resin A11> Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1) :22.6 parts (41.1mol%) Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) :55.0 parts (29.5mol%) Terephthalic acid: 5.5 parts (5.6 mol%) Suberic acid: 16.0 parts (23.8 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts Gallic acid (cocatalyst): 0.1 parts

[0163] The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the reaction vessel was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the reaction was carried out at 200°C for 2 hours with stirring.

[0164] The pressure in the reaction vessel was then lowered to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200°C. After it was confirmed that the weight average molecular weight had reached 6700, the temperature was lowered to stop the reaction, yielding an amorphous resin A11 having a polyethylene terephthalate structural portion in its molecule. The physical properties of the amorphous resin A11 obtained by the above-mentioned measurement method included an SP value of 11.30 (cal / cm 3 ) 0.5 , W EG 20.8 mol%, W CH The Tg was 48.5°C.

[0165] [Table 1-1]

[0166] [Table 1-2]

[0167] [Table 1-3]

[0168] The abbreviations in Tables 1-1 to 1-3 are as follows: BPA-PO: Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) BPA-EO: Ethylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol)

[0169] <Preparation of amorphous resin B1> Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1) :4.1 parts (9.8mol%) Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol) :57.8 parts (42.8mol%) Terephthalic acid: 29.9 parts (41.9 mol%) Trimellitic acid: 7.0 parts (4.5 mol%) Stearic acid: 1.2 parts (1.0 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts Gallic acid (cocatalyst): 0.1 parts

[0170] The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the reaction vessel was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the mixture was allowed to react at 200°C for 2 hours with stirring.

[0171] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200°C. After it was confirmed that the weight-average molecular weight had reached 1000, the temperature was reduced to stop the reaction, yielding amorphous resin B1. The physical properties of amorphous resin B1 obtained by the above-mentioned measurement methods are shown in Table 2.

[0172] <Preparation of amorphous resins B2 to B5> Amorphous resins B2 to B5 were obtained by carrying out the reaction in the same manner as in the preparation of amorphous resin B1, except that the parts amounts of polyethylene terephthalate and polymerizable monomer were changed as shown in Table 2. The physical properties of amorphous resins B2 to B5 obtained by the above-mentioned measurement methods are shown in Table 2.

[0173] [Table 2]

[0174] The abbreviations in Table 2 are as follows: BPA-PO: Propylene oxide adduct of bisphenol A (average number of moles added: 2.0 mol)

[0175] <Preparation 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

[0176] The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the reaction vessel was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the reaction was carried out at 200°C for 2 hours with stirring.

[0177] The pressure in the reaction vessel was then reduced to 8.3 kPa, and the reaction was continued for 5 hours while maintaining the temperature at 200°C. The temperature was then lowered to stop the reaction, yielding crystalline polyester C1. The physical properties of crystalline polyester C1 obtained by the above-mentioned measurement methods are shown in Table 3.

[0178] <Preparation of Crystalline Polyesters C2 to C5> Crystalline polyesters C2 to C5 were obtained by carrying out the reaction in the same manner as in the preparation of crystalline polyester C1, except that the types and parts of the polymerizable monomers, aliphatic monocarboxylic acids, or aliphatic monoalcohols were changed as shown in Table 3. The physical properties of crystalline polyesters C2 to C5 obtained by the above-mentioned measurement methods are shown in Table 3.

[0179] [Table 3]

[0180] <Toner 1 manufacturing example> Amorphous resin A1: 66 parts ·Amorphous resin B1: 34 parts Crystalline polyester C1: 10 parts Fischer-Tropsch wax (maximum endothermic peak temperature 100°C): 5 parts Carbon black: 5 parts Trisodium phosphate: 0.160 parts

[0181] The above materials were mixed using a Henschel mixer (FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for 5 minutes, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 130°C. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a Faculty (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11000 rpm and a dispersing rotor rotation speed of 7200 rpm. Toner particles 1:95 parts Large inorganic particles: Fumed silica surface-treated with hexamethyldisilazane (Median diameter (D50) based on number is 120 nm) 4 parts Small inorganic particles: Titanium oxide particles surface-treated with isobutyltrimethoxysilane (Median diameter (D50) based on number is 10 nm) 1 part

[0182] The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes to obtain negatively charged toner 1. The physical properties of toner 1 obtained by the above-mentioned measurement methods are shown in Table 4.

[0183] <Toner 2-35 manufacturing example> Toners 2 to 35 were obtained in the same manner as in Production Example of Toner 1, except that the types and parts of amorphous resin A, amorphous resin B, crystalline polyester C, and additives were changed as shown in Table 4. The physical properties of Toners 2 to 35 obtained by the above-mentioned measurement methods are shown in Table 4.

[0184] [Table 4]

[0185] The abbreviations in Table 4 are as follows: PNa: trisodium phosphate PF: Triphenyl phosphate SP A -SP C : [SP value of amorphous resin A (cal / cm 3 ) 0.5 ]-[SP value of crystalline polyester C (cal / cm 3 ) 0.5 ] W B / W A : [Parts by mass of amorphous resin B] / [Parts by mass of amorphous resin A]

[0186] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite2

[0187] To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles. Phenol: 10% by weight Formaldehyde solution: 6% by mass (Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass%

[0188] 100 parts of the above material, 5 parts of 28% by weight aqueous ammonia, and 20 parts of water were placed in a flask, stirred, and heated to 85°C over 30 minutes. The mixture was then maintained for 3 hours to polymerize and harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain spherical magnetic carrier 1 with dispersed magnetic material. The volume-based 50% particle size (D50) was 34.21 μm.

[0189] <Manufacturing example of two-component developer 1> 92.0 parts of magnetic carrier 1 and 8.0 parts of toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1.

[0190] <Production examples of two-component developers 2 to 35> In the production example of two-component developer 1, the same procedure was carried out except for the changes shown in Table 5, to obtain two-component developers 2 to 35.

[0191] Example 1 The above two-component developer 1 was used for evaluation.

[0192] The image forming apparatus used was a modified Canon imagePress C800 digital commercial printing printer, and two-component developer 1 was placed in the cyan developer. The modifications to the apparatus included the fixing temperature, process speed, and DC voltage V of the developer carrier. DC , the charging voltage V of the electrostatic latent image carrier D The image output evaluation was carried out by outputting a FFh image (solid image) with the desired image ratio, and adjusting V so that the amount of toner on the FFh image on the paper was the desired amount. DC , V D The evaluation described below was performed by adjusting the value and laser power. FFh is a value representing 256 gradations in hexadecimal, with 00h being the first gradation of 256 gradations (white background) and FFh being the 256th gradation of 256 gradations (solid area). Evaluation was performed based on the following evaluation method, and the results are shown in Table 5.

[0193] [Scratch resistance] Paper: UPM FINESSE GLOSS 300GSM Toner amount on paper: 0.05 mg / cm 2 (2Fh image) (The amount of toner carried is determined by the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 3cm x 15cm image placed in the center of the A4 paper. Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50% RH (hereinafter referred to as N / N)) Fixing temperature: 180℃ Process speed: 377 mm / sec

[0194] The above evaluation image was printed and the scratch resistance was evaluated. Specifically, a surface property tester, HEIDON TYPE14FW, manufactured by Shinto Scientific Co., Ltd., was used to place a 200g weight on the image and scratch it with a 0.75mm diameter needle at a speed of 60mm / min and a length of 30mm, and the scratch resistance was evaluated based on the scratches that appeared on the image. The area ratio of toner peeled was calculated by binarizing the area where toner peeled occurred relative to the scratched area using image processing.

[0195] (Evaluation criteria) A: 0.0% B: 0.1% or more and less than 0.4% C: 0.4% or more and less than 0.9% D: 0.9% or more and less than 1.1% E: 1.1% or more

[0196] [Low temperature fixability] Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.50 mg / cm 2 (The amount of toner carried is determined by the DC voltage V DC , the charging voltage V of the electrostatic latent image carrier D, and adjusted by laser power) Evaluation image: A 2cm x 5cm image placed in the center of the A4 paper. Test environment: Low temperature and humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") Fixing temperature: 150℃ Process speed: 630 mm / sec

[0197] The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the rate of decrease in image density was used as an evaluation index for the low-temperature fixability.

[0198] First, the image density at the center was measured using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite). Next, the area where the image density was measured was subjected to a pressure of 4.9 kPa (50 g / cm). 2 The fixed image was rubbed (five times back and forth) with Silbon paper under a load of 1000 kJ / cm2, and the image density was measured again.

[0199] The rate of decrease in image density before and after rubbing was calculated using the following formula. The obtained rate of decrease in image density was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good. Image density reduction rate (%) = (image density before friction - image density after friction) / image density before friction x 100

[0200] (Evaluation criteria) A: Image density reduction rate less than 3% B: Image density reduction rate: 3% to less than 5% C: Image density reduction rate: 5% to less than 8% D: Image density reduction rate: 8% or more but less than 10% E: Image density reduction rate 10% or more

[0201] <Examples 2 to 27 and Comparative Examples 1 to 8> Except for using two-component developers 2 to 35, evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 5.

[0202] [Table 5]

[0203] The present disclosure provides a toner that exhibits excellent low-temperature fixability and scratch resistance. Because the toner of the present disclosure can use polyethylene terephthalate recycled from used PET bottles and the like as a toner material, the technology described herein can contribute to the realization of a sustainable society, such as a decarbonized / recycling-based society.

[0204] The present disclosure relates to the following configurations.

[0205] (Configuration 1) A toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The amorphous resin A is a polyester, and the structure forming the polyester skeleton is (i) a polyethylene terephthalate structure, and (ii) at least one structure selected from the group consisting of a unit represented by the following formula (1), a unit represented by the following formula (2), a unit represented by the following formula (3), and a unit represented by the following formula (4): and

[0206] [ka]

[0207] (In formula (1), R1 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A1 represents a hydrocarbon group; * represents a bond in the polyester backbone, m represents an integer of 2 or greater.

[0208] [ka]

[0209] (In formula (2), R2 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B1 represents a hydrocarbon group; * represents a bond in the polyester backbone, n represents an integer of 2 or greater.

[0210] [ka]

[0211] (In formula (3), * represents a bond in the polyester skeleton, x represents an integer of 6 to 16.

[0212] [ka]

[0213] (In formula (4), * represents a bond in the polyester skeleton, y represents an integer from 6 to 16.

[0214] The SP value of the amorphous resin A is A (cal / cm 3 ) 0.5 The SP value of the crystalline polyester C is SP C (cal / cm 3 ) 0.5 When this is done, the SP A and the SP C and satisfy the following formula (C), 1.00≦SP A -SP C ≦1.35 (C) the toner contains a phosphorus element derived from a phosphorus compound, The content of the phosphorus element in the toner based on the mass of the toner is W P (ppm), the W P A toner characterized in that the following formula (D) is satisfied: 5≦W P ≦500 (D)

[0215] (Configuration 2) The W P The toner according to configuration 1, wherein the following formula (K) is satisfied: 20≦W P ≦500 (K)

[0216] (Configuration 3) The ratio of the structure derived from ethylene glycol in the polyethylene terephthalate structure to the total number of moles of the structure derived from alcohol and the structure derived from carboxylic acid that form the polyester skeleton in the amorphous resin A is W EG (mol%), the W EG 3. The toner according to claim 1, wherein the following formula (E) is satisfied: 12.6≦W EG ≦24.8 (E)

[0217] (Configuration 4) The total ratio of the units represented by the formula (1), the units represented by the formula (2), the units represented by the formula (3), and the units represented by the formula (4) to the total number of moles of the structures derived from alcohols and the structures derived from carboxylic acids that form the polyester skeleton in the amorphous resin A is W CH (mol%), the W CH 4. The toner according to any one of configurations 1 to 3, wherein the following formula (F) is satisfied: 5.6≦W CH ≦14.6 (F)

[0218] (Configuration 5) 5. The toner according to any one of Configurations 1 to 4, wherein the crystalline polyester C is a modified crystalline polyester having a structure in which a hydroxy group at a terminal of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or a modified crystalline polyester having a structure in which a carboxy group at a terminal of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms.

[0219] (Configuration 6) 6. The toner according to any one of configurations 1 to 5, wherein the amorphous resin A contains a unit represented by formula (1) or a unit represented by formula (2).

Claims

1. A toner having toner particles containing a binder resin, The binder resin contains an amorphous resin A and a crystalline polyester C, The amorphous resin A is a polyester, and the structure forming the polyester skeleton is (i) a polyethylene terephthalate structure, and (ii) at least one structure selected from the group consisting of a unit represented by the following formula (1), a unit represented by the following formula (2), a unit represented by the following formula (3), and a unit represented by the following formula (4): and 【Chemical 1】 (In formula (1), R1 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A1 represents a hydrocarbon group; * represents a bond in the polyester backbone, m represents an integer of 2 or more. 【Chemistry 2】 (In formula (2), R2 represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B1 represents a hydrocarbon group; * represents a bond in the polyester backbone, n represents an integer of 2 or more. 【Chemistry 3】 (In formula (3), * represents a bond in the polyester skeleton, x represents an integer of 6 to 16. 【Chemistry 4】 (In formula (4), * represents a bond in the polyester skeleton, y represents an integer of 6 to 16. The SP value of the amorphous resin A is Ａ (cal / cm ３ ) ０．５ The SP value of the crystalline polyester C is Ｃ (cal / cm ３ ) ０．５ When this is the case, the SP Ａ and the SP Ｃ and satisfy the following formula (C), 1.00≦SP Ａ -SP Ｃ ≦1.35・・・(C) the toner contains a phosphorus element derived from a phosphorus compound, The content of the phosphorus element in the toner based on the mass of the toner is W Ｐ (ppm), the W Ｐ A toner characterized in that the following formula (D) is satisfied: 5≦W Ｐ ≦500・・・(D)

2. The W Ｐ The toner according to claim 1, wherein the following formula (K) is satisfied: 20≦W Ｐ ≦500・・・(K)

3. The ratio of the structure derived from ethylene glycol in the polyethylene terephthalate structure portion to the total number of moles of the structure derived from alcohol and the structure derived from carboxylic acid that form the polyester skeleton in the amorphous resin A is W ＥＧ (mol %), the W ＥＧ 3. The toner according to claim 1, wherein the following formula (E) is satisfied: 12.6≦W ＥＧ ≦24.8・・・(E)

4. The total ratio of the units represented by the formula (1), the units represented by the formula (2), the units represented by the formula (3), and the units represented by the formula (4) to the total number of moles of the structures derived from alcohols and the structures derived from carboxylic acids that form the polyester skeleton in the amorphous resin A is W ＣＨ (mol %), the W ＣＨ The toner according to claim 1 or 2, wherein the following formula (F) is satisfied: 5.6≦W ＣＨ ≦14.6・・・(F)

5. The toner according to claim 1 or 2, wherein the crystalline polyester C is a modified crystalline polyester having a structure in which a hydroxy group at a terminal of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or a modified crystalline polyester having a structure in which a carboxy group at a terminal of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms.

6. 3. The toner according to claim 1, wherein the amorphous resin A contains a unit represented by formula (1) or a unit represented by formula (2).

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