toner

Abstract

To provide a toner which is excellent in light resistance even when a coloring agent having an azo group is used.SOLUTION: A toner contains toner particles. The toner particles contain a coloring agent having resin A, resin B and an azo group. The resin A has a substituted or unsubstituted silyl group in a molecule, a substituent group of the substituted silyl group is at least one selected from a group composed of an alkyl group whose carbon atom number is 1 or larger, an alkoxy group whose carbon atom number is 1 or larger, a hydroxy group, a halogen atom, and an aryl group whose carbon atom number is 6 or larger. Content of the silicon atom in the resin A ranges from 0.02 mass % to 10.00 mass %, and the resin B has a monovalent group having a salicylic acid structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to toners for developing electrostatic images used in imaging processes such as electrophotography and electrostatic printing. [Background technology]

[0002] In recent years, electrophotography has been actively applied to production printing and photographic printing, and accordingly, in electrophotographic image formation, high image quality, high developability, and high light resistance, which are essential elements for production printing and photographic printing, have been strongly demanded. When forming a full-color image using an electrophotographic method, it is common to form the full-color image by subtractive color mixing using yellow, cyan, magenta, and black toners. To achieve high image quality using this method, it is necessary to control the mixing ratio of each color so that the desired color can be expressed under any environment. To achieve this, studies are being conducted to improve the chargeability of the toner. In addition, there is a demand for achieving high coloring power and a wide color gamut, and studies are being conducted to use pigments that have good dispersibility in toner and can easily achieve high coloring power and a wide color gamut. Azo pigments are being widely studied because of their excellent color gamut and coloring power. Patent Document 1 proposes a toner that combines a resin having a specific acid dissociation constant pKa with a colorant having an azo group, thereby exhibiting high color reproducibility and charging characteristics with excellent environmental stability, and having high image reproducibility in various environments. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-173813 Summary of the Invention [Problem to be solved by the invention]

[0004] However, although colorants containing azo groups have excellent color gamut and coloring strength, it has been found that when printed images are exposed to light for a long period of time, the azo groups are cleaved and the conjugated system is lost, resulting in color fading. The present disclosure provides a toner that has excellent light resistance even when a colorant having an azo group is used. [Means for solving the problem]

[0005] The present disclosure provides a toner comprising toner particles, The toner particles Binder resin, Contains resin A, resin B, and a colorant having an azo group, the content of the resin A relative to 100.0 parts by mass of the binder resin in the toner particles is 0.1 parts by mass to 20.0 parts by mass, the content of the resin B relative to 100.0 parts by mass of the binder resin in the toner particles is 0.1 parts by mass to 20.0 parts by mass, The binder resin does not have a silyl group or a salicylic acid skeleton, The resin A is A structure represented by the following formula (1) have 、 the content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass, The resin B 、 Contains a monovalent group with a salicylic acid structure The present invention relates to a toner characterized by the above-mentioned. TIFF0007746113000001.tif37170 (In the formula (1), P 1 represents the polyester resin portion, and L 1 represents a single bond or a divalent linking group, R 1 ~R 3 are each independently a hydrogen atom, a halogen atom, or a group having one or more carbon atoms. represents an alkyl group, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxy group; m represents a positive integer; and when m is 2 or more, a plurality of L 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different.) [Effects of the Invention]

[0006] According to the present disclosure, a toner having excellent light resistance can be provided even when a colorant having an azo group is used. [Brief explanation of the drawings]

[0007] [Figure 1] Example of a device for measuring charge amount DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit. When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0009] The present disclosure provides a toner comprising toner particles, the toner particles contain a resin A, a resin B, and a colorant having an azo group, The resin A has a substituted or unsubstituted silyl group in the molecule, the substituent of the substituted silyl group is at least one selected from the group consisting of an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, a hydroxy group, a halogen atom, and an aryl group having six or more carbon atoms; The content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass, and the resin B has a monovalent group having a salicylic acid structure. The present invention relates to a toner characterized by the above-mentioned.

[0010] The present inventors have found that by employing the toner having the above-described configuration, it is possible to provide a toner having excellent light resistance even when a colorant having an azo group is used. The reason for this is speculated as follows. It is known that the mechanism behind the fading of colorants is that active oxygen generated by exposure to sunlight reacts with the colorant. Active oxygen species include superoxide, hydrogen peroxide, and hydroxyl radicals. Given their half-life, hydroxyl radicals are particularly highly reactive, so we will use hydroxyl radicals as an example. Water is a source of active oxygen present in printed images. When high energy is incident on water, ionization of water molecules occurs as shown in formula (a). It is known that subsequent reaction with surrounding water generates hydrated electrons and hydroxyl radicals as shown in formulas (b) and (c). H2O → H2O + +e - (a) e - →e - aq (b) H2O++H2O→H3O + + OH (c)

[0011] In this way, the reactions of formulas (a) to (c) occur consecutively, and the generated hydroxyl radicals attack and decompose the azo groups of the colorant, which is thought to cause fading. However, if the water molecule ions generated in formula (a) recombine with electrons, the reaction leading to the generation of subsequent hydroxyl radicals is suppressed, and fading of the colorant can be suppressed.

[0012] The toner particles contain resin A and resin B. Resin A has a silyl group. Silicon atoms are polarized due to their low electronegativity, and therefore carry a positive charge. This is thought to capture the electrons generated in the above formula (a). Resin B also has a monovalent group with a salicylic acid structure, which carries a negative charge. This is thought to capture the water molecule ions generated in the above formula (a). Because the silicon atoms of resin A and resin B have opposite polarities, they are electrostatically attracted to each other, and the two are thought to be in close proximity within the toner particles. Rapid electron transfer occurs between resin A and resin B, which are in close proximity, and the water molecule ions and electrons captured by each recombine and return to water, which is thought to suppress the generation of hydroxyl radicals. As a result, the colorant is not attacked by hydroxy radicals and does not decompose, maintaining lightfastness. In the present invention, by setting the silicon atom content in resin A to 0.02 mass % or more, electron capture and charge transfer to resin B occur smoothly, and it is believed that the above-mentioned effects are achieved.

[0013] Here, when opposite polarities are in close proximity, it is thought that the charges will cancel each other out. However, Resin A only has partially polarized silicon atoms in its molecule, and the molecule as a whole does not have a positive charge, so it does not impede the chargeability of the entire toner. For this reason, Resin A is used instead of simply a positively charged resin.

[0014] <Resin A> The toner particles contain a resin A. The resin A is preferably an organic resin. Resin A (i) has a substituted or unsubstituted silyl group in the molecule, and (ii) the substituent of the substituted silyl group is at least one selected from the group consisting of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, a hydroxy group, a halogen atom, and an aryl group having 6 or more carbon atoms. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms. The aryl group preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The content of silicon atoms in Resin A is 0.02% by mass to 10.00% by mass. By setting the content to 0.02% by mass or more, light resistance is improved as described above. Furthermore, by setting the content to 10.00% by mass or less, charge leakage under high temperature and high humidity conditions can be suppressed. The content of silicon atoms in Resin A is preferably 0.20% by mass to 5.00% by mass. The content of silicon atoms in the resin A can be controlled by adjusting the amount of silicon compound used in producing the resin A. Preferred examples of resin A are not limited as long as they satisfy the above (i) and (ii), but include resins chemically bonded with silane coupling agents or the like, polymers of organosilicon compounds, and hybrid resins thereof. More specifically, examples include resins obtained by modifying polyester resins, vinyl resins, polycarbonate resins, polyurethane resins, phenolic resins, epoxy resins, polyolefin resins, or styrene-acrylic resins with silane coupling agents and / or silicone oils.

[0015] Resin A preferably has a structure represented by the following formula (1): This improves the electron capturing ability and the charge transfer efficiency to resin B, thereby significantly improving light resistance.

[0016] [ka]

[0017] (In the formula (1), P 1 represents the polymer moiety, and L 1 represents a single bond or a divalent linking group, R 1 ~R 3each independently represents a hydrogen atom, a halogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, an aryl group having six or more carbon atoms, or a hydroxy group; m represents a positive integer, and when m is 2 or more, 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different.)

[0018] R in the formula (1) 1 ~R 3 At least one of the R in the formula (1) preferably represents an alkoxy group having one or more carbon atoms or a hydroxy group. 1 ~R 3 each independently represents an alkoxy group having one or more carbon atoms or a hydroxy group. It is believed that by bonding an electron-withdrawing alkoxy group or hydroxy group to a silicon atom, the positive charge of the silicon atom becomes stronger, the electron-capturing ability increases, and light resistance is further improved.

[0019] Of the above substituents, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 4. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2. Within this range, the electron-withdrawing property is excellent. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10. When the above substituents are within these ranges, the silicon atom is better polarized.

[0020] The content of resin A in the toner particles is preferably 0.05% by mass to 90.0% by mass, more preferably 0.05% by mass to 10.0% by mass, even more preferably 0.1% by mass to 8.0% by mass, and particularly preferably 0.5% by mass to 6.0% by mass.

[0021] R in the formula (1)1 ~R 3 To make one or more of R into a hydroxy group, 1 ~R 3 Resin A in which one or more of the above groups are alkoxy groups may be hydrolyzed to convert the alkoxy groups into hydroxy groups. Any method for hydrolysis may be used, but examples include the following. R in the formula (1) 1 ~R 3 Resin A, in which one or more of the above groups are alkoxy groups, is dissolved or suspended in a suitable solvent (which may be a polymerizable monomer), and the pH is adjusted to acidic using an acid or alkali, followed by mixing and hydrolysis. Further, hydrolysis may be caused during the production of toner particles.

[0022] P in the formula (1) 1 Examples of the resin moiety include, but are not limited to, polyester resin moieties, vinyl resin moieties, styrene acrylic resin moieties, polyurethane resin moieties, polycarbonate resin moieties, phenolic resin moieties, polyolefin resin moieties, and the like. Among these, P is the best because it transfers charge well to resin B. 1 More preferably, P represents a polyester resin moiety or a styrene acrylic resin moiety. 1 may be a hybrid resin moiety of polyester resin and styrene-acrylic resin. 1 More preferably, represents a styrene acrylic resin moiety. P 1 When the resin is a styrene acrylic resin moiety, the water content is low and the source of active oxygen can be reduced, which is effective in further improving light resistance.

[0023] The weight average molecular weight (Mw) of resin A is preferably 3,000 or more and 100,000 or less, more preferably 8,000 or more and 30,000 or less, from the viewpoints of affinity with resin B and charge transfer. The Mw of the resin A can be controlled by various methods depending on the type of resin contained. For example, when a polyester resin is contained, it can be controlled by adjusting the charging ratio of its monomers, dialcohol and dicarboxylic acid, or by adjusting the polymerization time. Furthermore, when a styrene-acrylic resin is contained, it can be controlled by adjusting the ratio of its monomer, vinyl monomer, and polymerization initiator, or by adjusting the reaction temperature.

[0024] The polyester resin is not particularly limited, but is preferably a condensate of a dialcohol and a dicarboxylic acid. For example, a polyester resin having a structure represented by the following formula (6) and at least one structure (multiple structures can be selected) selected from the group consisting of structures represented by the following formulas (7) to (9) is preferred. Alternatively, a polyester resin having a structure represented by the following formula (10) is also preferred.

[0025] [ka]

[0026] (In formula (6), R 9 represents an alkylene group, an alkenylene group, or an arylene group. 10 represents an alkylene group or a phenylene group. 18 represents an ethylene group or a propylene group. x and y are each an integer of 0 or more, and the average value of x+y is 2 to 10. In formula (10), R 11 represents an alkylene group or an alkenylene group.

[0027] R in the above formula (6) 9 Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in the formula (I) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group. R in the above formula (6) 9 Examples of the alkenylene group (preferably having 2 to 4 carbon atoms) in the formula include a vinylene group, a propenylene group, and a 2-butenylene group. R in the above formula (6) 9 Examples of the arylene group (preferably having 6 to 12 carbon atoms) in the formula include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2,6-naphthylene group, a 2,7-naphthylene group, and a 4,4'-biphenylene group. R in the above formula (6) 9 may be substituted with a substituent, in which case, examples of the substituent include a methyl group, a halogen atom, a carboxy group, a trifluoromethyl group, and combinations thereof.

[0028] R in the above formula (7) 10 Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in the formula (I) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene group. R in the above formula (7) 10 Examples of the phenylene group in the formula include a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group. R in the above formula (7) 10 may be substituted with a substituent, in which case, examples of the substituent include a methyl group, an alkoxy group, a hydroxy group, a halogen atom, and combinations thereof.

[0029] R in the above formula (10) 11Examples of the alkylene group (preferably having 1 to 12 carbon atoms) in the formula (I) include the following: methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, hexamethylene group, neopentylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, and 1,4-cyclohexylene group. R in the above formula (10) 11 Examples of the alkenylene group (preferably having 2 to 40 carbon atoms) in the formula (1) include the following: vinylene group, propenylene group, butenylene group, butadienylene group, pentenylene group, hexenylene group, hexadienylene group, heptenylene group, octanylene group, decenylene group, octadecenylene group, eicosenylene group, and triacontenylene group. These alkenylene groups may have a linear, branched, or cyclic structure. The double bond may be located anywhere, as long as there is at least one double bond. R in the above formula (10) 11 may be substituted with a substituent, in which case the substituent may be an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a combination thereof.

[0030] The styrene-acrylic resin and vinyl resin are not particularly limited and known ones can be used. For example, the following monomers can be used. Styrenic monomers such as styrene and derivatives thereof, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, and pn-dodecylstyrene. acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate.

[0031] Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl monomers containing nitrogen atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. Vinyl monomers containing a carboxy group, such as unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, and mesaconic acid; α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; and acid anhydrides thereof.

[0032] L as a linking group 1 In order to form the above, the styrene-acrylic resin or vinyl resin may contain a carboxy group. The method for incorporating a carboxy group into a styrene-acrylic resin or a vinyl resin is not particularly limited, and any known method can be used. For example, it is preferable to use a vinyl monomer containing a carboxy group, such as acrylic acid or methacrylic acid. The styrene-acrylic resin in the styrene-acrylic resin portion is preferably a polymer of at least one selected from the group consisting of acrylic acid esters and methacrylic acid esters, a styrene-based monomer, and a vinyl-based monomer containing a carboxy group.

[0033] L in the formula (1) 1 Examples of the divalent linking group that can be represented include structures represented by the following formulas (2) to (5), but are not particularly limited to these.

[0034] [ka]

[0035] (R in Equation (2) 5 represents a single bond, an alkylene group, or an arylene group. (*) represents P in formula (1). 1 represents the bonding site to the silicon atom in formula (1), and (**) represents the bonding site to the silicon atom in formula (1). R in equation (3) 6 represents a single bond, an alkylene group, or an arylene group. (*) represents P in formula (1). 1 represents the bonding site to the silicon atom in formula (1), and (**) represents the bonding site to the silicon atom in formula (1). R in formulas (4) and (5) 7 and R 8 Each of the (*) represents an alkylene group, an arylene group, or an oxyalkylene group. 1 represents the bonding site to the silicon atom in formula (1), and (**) represents the bonding site to the silicon atom in formula (1).

[0036] The structure represented by the formula (2) is a divalent linking group containing an amide bond. The linking group can be formed, for example, by reacting a carboxy group in the resin with an aminosilane. The aminosilane is not particularly limited, but examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, and 3-aminopropylsilane. R 5 The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an alkylene group containing an —NH— group. R 5 The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an arylene group containing a hetero atom.

[0037] The structure represented by the formula (3) is a divalent linking group containing a urethane bond. The linking group can be formed, for example, by reacting a hydroxy group in the resin with an isocyanate silane. The isocyanate silane is not particularly limited, but examples thereof include 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl dimethoxy silane, 3-isocyanate propyl dimethyl methoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl diethoxy silane, and 3-isocyanate propyl dimethyl ethoxy silane. R 6 The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an alkylene group containing an —NH— group. R 6The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an arylene group containing a hetero atom.

[0038] The structure represented by the formula (4) or (5) is a divalent linking group containing a bond grafted to an ester bond in the resin. The linking group is formed, for example, by an insertion reaction of an epoxysilane. The insertion reaction of epoxysilane refers to a reaction that includes a step of inserting the epoxy group of epoxysilane into the ester bond in the main chain of a resin. The insertion reaction referred to here refers to the reaction described as "insertion reaction of an epoxy compound into an ester bond in a polymer chain" in Organic Synthetic Chemistry, Vol. 49, No. 3, p. 218, 1991. The reaction mechanism of the epoxysilane insertion reaction can be represented by the following model diagram.

[0039] [ka]

[0040] (In the figure, D and E represent the constituent parts of the resin, and F represents the constituent part of the epoxy compound.) In the diagram, the ring-opening of the epoxy group can be either α-cleavage or β-cleavage, resulting in two types of compounds. In either case, the epoxy group is inserted into the ester bond in the resin; in other words, the components of the epoxy compound other than the epoxy moiety are grafted onto the resin. The epoxy silane is not particularly limited, but examples thereof include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and the like.

[0041] R 7 and R 8The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an alkylene group containing an —NH— group. R 7 and R 8 The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an arylene group containing a hetero atom. R 7 and R 8 The oxyalkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in the formula (I) is not particularly limited, and may be, for example, an oxyalkylene group containing an —NH— group.

[0042] <Resin B> Resin B is a resin having a monovalent group having a salicylic acid structure. The monovalent group having a salicylic acid structure preferably has a structure represented by the following formula (16).

[0043] [ka]

[0044] (In formula (16), R 19 represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms (more preferably 1 to 10 carbon atoms), or an alkoxy group having 1 to 18 carbon atoms (more preferably 1 to 3 carbon atoms), and h represents an integer of 0 to 3. When h is 2 or 3, h R 19 may be the same or different.) R 19 Examples of the alkyl group in the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the oxy group include a methoxy group, an ethoxy group, and a propoxy group. A more preferred structure of the monovalent group represented by formula (16) is R 19represents an alkyl group having 1 to 18 carbon atoms (more preferably 1 to 10 carbon atoms) or an alkoxy group having 1 to 18 carbon atoms (more preferably 1 to 3 carbon atoms), and h represents 0 or 1.

[0045] The monovalent group having a salicylic acid structure more preferably has a structure represented by the following formula (17), because having this structure strengthens the interaction with the colorant and further enhances the effect of improving lightfastness.

[0046] [ka]

[0047] (In formula (17), R 19 represents a hydroxy group, a carboxy group, an alkyl group having 1 to 18 carbon atoms (more preferably 1 to 10 carbon atoms), or an alkoxy group having 1 to 18 carbon atoms (more preferably 1 to 3 carbon atoms), and R 20 represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms, g represents an integer of 1 to 3, and h represents an integer of 0 to 3. When h is 2 or 3, there are h R 19 may be the same or different.) R 20 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. In formula (17), the more preferred structure is R 19 represents an alkyl group having 1 to 18 carbon atoms (more preferably, 1 to 10 carbon atoms) or an alkoxy group having 1 to 18 carbon atoms (more preferably, 1 to 3 carbon atoms); R 20 represents a hydrogen atom, g represents 1 or 2, and h represents 0 or 1.

[0048] There are no particular limitations on the main chain structure of Resin B. Examples include vinyl resins, polyester resins, polyamide resins, polyurethane resins, and polyether resins. Also included are hybrid resins that combine two or more of these, such as a hybrid resin of a polyester resin and a vinyl resin. Among these, resin B is preferably a polyester resin having a monovalent group with a salicylic acid structure or a vinyl resin having a monovalent group with a salicylic acid structure, which allows efficient transfer of charges between resin A and resin B. The vinyl resin is preferably a styrene-acrylic resin. That is, Resin B is more preferably a polyester resin having a monovalent group with a salicylic acid structure or a styrene-acrylic resin having a monovalent group with a salicylic acid structure. More preferably, Resin B is a vinyl resin (more preferably a styrene-acrylic resin) having a monovalent group with a salicylic acid structure. Even more preferably, Resin B is a vinyl resin (more preferably a styrene-acrylic resin) having a monovalent group represented by formula (17) as the following structure (18).

[0049] [ka]

[0050] (In formula (18), R 19 , R 20 , g, and h are the same as in equation (17). 22 represents a hydrogen atom or a methyl group. 22 The brackets containing indicate the main chain structure of the vinyl polymer.

[0051] The weight average molecular weight of Resin B calculated by gel permeation chromatography (GPC) is preferably 5,000 or more and 100,000 or less, and more preferably 20,000 or more and 40,000 or less. Within this range, affinity with resin A is good, facilitating charge transfer. The weight-average molecular weight can be controlled to fall within the above range by changing conditions such as the amount of reagents, reaction temperature, and solvent concentration when producing resin B. Furthermore, resin B with the desired molecular weight can be obtained by separating and fractionating using GPC.

[0052] The content of the monovalent group represented by structural formula (17) in resin B is preferably 50 μmol / g or more and 1000 μmol / g or less, and more preferably 200 μmol / g or more and 700 μmol / g or less. By setting it in this range, good charge transfer with resin A can be achieved.

[0053] The method for producing Resin B is not particularly limited, and Resin B can be produced by a known method. In the case of a vinyl polymer, for example, it is a method of copolymerizing a polymerizable monomer represented by formula (19) or formula (20) with a vinyl monomer using a polymerization initiator.

[0054] [ka]

[0055] (In the formula, R 19 and h are the same as in equation (16). 24 represents a hydrogen atom or a methyl group.

[0056] [ka]

[0057] (In the formula, R 19 , R 20 , g, and h are the same as in equation (17). 23 represents a hydrogen atom or a methyl group.

[0058] The vinyl monomer to be copolymerized with the polymerizable monomer represented by formula (19) or formula (20) is not particularly limited. Specific examples include styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, and vinyl benzoate; acrylic esters such as n-butyl acrylate and 2-ethylhexyl acrylate; methacrylic esters in which the acryl of the above acrylic esters is changed to methacrylic; methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinylpyrrole; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; acrylic acid; and methacrylic acid. Two or more types of vinyl monomers may be used in combination as needed.

[0059] Resin B is preferably a copolymer of a (meth)acrylic acid ester having 1 to 12 carbon atoms (more preferably 4 to 10), styrene, and a polymerizable monomer represented by formula (19) or formula (20). Resin B is more preferably a copolymer of an acrylic acid ester having 1 to 12 carbon atoms (more preferably 4 to 10), styrene, and a polymerizable monomer represented by formula (20).

[0060] On the other hand, when the resin B having the monovalent group represented by formula (16) or formula (17) is a polyester resin, various known production methods can be used. For example, I) A method of converting a reactive residue of a carboxyl group or a hydroxyl group contained in a polyester structure into a monovalent group represented by formula (16) or formula (17) by an organic reaction; II) A method for producing a polyester using a polyhydric alcohol or a polycarboxylic acid having a monovalent group represented by formula (16) or formula (17) as a substituent; III) A method in which a functional group that can easily introduce the monovalent group represented by formula (16) or formula (17) as a substituent into a polyhydric alcohol or a polycarboxylic acid is previously introduced; etc.

[0061] Also, if resin B is a hybrid resin, IV) A method of hybridizing a polyester resin containing a monovalent group represented by formula (16) or formula (17) as a substituent with a vinyl monomer; V) As a vinyl monomer, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is used. and then converting the carboxy group into a structure represented by formula (16) or formula (17) by an organic reaction; VI) A method of hybridizing a polyester resin using a polymerizable monomer represented by formula (19) or formula (20); etc.

[0062] The content of resin B in the toner particles is preferably 0.01% by mass to 50.0% by mass, more preferably 0.05% by mass to 10.0% by mass, even more preferably 0.1% by mass to 8.0% by mass, and even more preferably 0.5% by mass to 6.0% by mass.

[0063] The mass ratio of the content of resin A to the content of resin B in the toner (resin A / resin B) is preferably 0.05 or more and 50.00 or less. Within this range, charge transfer between resin A and resin B occurs efficiently, and generation of active oxygen species can be suppressed, resulting in better light resistance. More preferably, it is 0.25 or more and 20.00 or less.

[0064] The toner particles may contain a binder resin. When the toner particles contain a binder resin, the content of resin A relative to 100.0 parts by mass of the binder resin is preferably 0.1 to 20.0 parts by mass, more preferably 0.1 to 5.0 parts by mass. Similarly, the content of resin B relative to 100.0 parts by mass of the binder resin is preferably 0.1 to 20.0 parts by mass, more preferably 0.1 to 5.0 parts by mass.

[0065] The binder resin is not particularly limited, and conventionally known resins can be used, but vinyl resins, polyester resins, etc. are preferred. Examples of vinyl resins, polyester resins, and other binder resins include the following resins or polymers. The vinyl resin is preferably a styrene-acrylic resin. The binder resin is a resin that does not have a silyl group. The binder resin is also a resin that does not have a salicylic acid skeleton.

[0066] Homopolymers of styrene and its substituted derivatives, such as polystyrene and polyvinyltoluene; Styrenic copolymers such as styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester copolymer; Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, and aromatic petroleum resin. These binder resins can be used alone or in combination of two or more.

[0067] From the viewpoint of chargeability, the binder resin preferably contains a carboxy group, and is preferably a resin produced using a polymerizable monomer containing a carboxy group. Specific examples of the polymerizable monomer containing a carboxy group include, but are not limited to, the following polymerizable monomers: (Meth)acrylic acids such as α-ethylacrylic acid and crotonic acid, and their α-alkyl or β-alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid; unsaturated dicarboxylic acid monoester derivatives such as succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyethylene ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester.

[0068] As the polyester resin, a resin obtained by polycondensation of a carboxylic acid component and an alcohol component as shown below can be used. Examples of the carboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. Examples of the alcohol component include bisphenol A, hydrogenated bisphenol, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

[0069] The polyester resin may also be a polyester resin containing a urea group. It is preferable that the carboxyl groups present at the terminals of the polyester resin are not capped. In order to improve the viscosity change of the toner at high temperatures, the binder resin may have a polymerizable functional group, such as a vinyl group, an isocyanate group, an epoxy group, an amino group, a carboxy group, or a hydroxy group.

[0070] In addition to the above, the vinyl resin or styrene-acrylic resin in the binder resin may also contain the same monomer as the styrene-acrylic resin moiety in Resin A. The binder resin is more preferably a copolymer of a (meth)acrylic acid ester having 1 to 8 carbon atoms (more preferably 2 to 6) and a monomer containing styrene.

[0071] The binder resin contains a styrene-acrylic resin moiety, and P in the formula (1) 1 It is preferable that represents a styrene acrylic resin moiety. It is more preferable that the binder resin is a styrene acrylic resin. In addition, the binder resin contains a polyester resin moiety, and P in the formula (1) 1 represents a polyester resin moiety. The binder resin is more preferably a polyester resin. The binder resin may be a hybrid resin having a styrene-acrylic resin and a polyester resin moiety.

[0072] Binder resin and P in formula (1) 1 It has been found that the inclusion of a common resin in the binder resin and the P in formula (1) has the effect of improving not only light resistance but also coloring power. 1 Since the results show that the dispersibility of colorants improves when the values ​​are consistent, we believe the following. Resin A is polarized at the silyl group, so it has a high affinity with highly polar colorants and exists in the vicinity of the colorants. In addition, because Resin A has the same components as the binder resin, it can be highly dispersed in the binder resin. For these reasons, the binder resin and P in formula (1) 1It is believed that this coincidence allows Resin A to exert its effect of dispersing the colorant in the binder resin.

[0073] The binder resin contains a polyester resin moiety, and P 1 represents a polyester resin moiety, and it is preferred that Resin B contains a polyester resin moiety. In addition, the binder resin contains a styrene-acrylic resin moiety, and P in the formula (1) 1 represents a styrene-acrylic resin moiety, and it is preferred that Resin B contains a styrene-acrylic resin moiety. It has been revealed that the above-mentioned configuration can suppress toner cracking in addition to improving light resistance.

[0074] Toner cracking is likely to occur when voids exist in the toner. It was found that when the binder resin, resin A, and resin B have a polyester resin portion or a styrene acrylic resin portion in common, there are fewer voids. The interaction with the colorant is strongest in the order of resin B, resin A, and binder resin, and it is thought that they exist around the colorant in that order. When these resins have polyester or styrene acrylic moieties in common, they mix well at the interface between the materials, which is thought to suppress the occurrence of voids.

[0075] <Coloring agent> The toner contains a colorant having an azo group. Examples of the colorant having an azo group include monoazo pigments, disazo pigments, and polyazo pigments. Examples include the following: CIPigment Yellow 74, 93, 128, 155, 180; CIPigment Orange 1, 5, 13, 15, 16, 34, 36, 38, 62, 64, 67, 72, 74; CIPigment Red 2, 3, 4, 5, 12, 16, 17, 23, 31, 32, 41, 17, 48, 48:1, 48:2, 53:1, 57:1, 112, 144, 146, 150, 166, 170, 176, 185, 187, 208, 210, 220, 221, 238, 242, 245, 253, 258, 266, 269; CIPigment Violet 13, 25, 32, 50; CIPigment Blue 25, 26; CIPigment Brown 23, 25, 41, etc.

[0076] Among these, the colorant having an azo group is preferably at least one selected from the group consisting of CI Pigment Yellow 74, CI Pigment Red 269, CI Pigment Yellow 155, CI Pigment Yellow 180, and CI Pigment Red 150. The colorant having an azo group is more preferably at least one selected from the group consisting of CI Pigment Yellow 155, CI Pigment Red 150, and CI Pigment Red 269.

[0077] <Crosslinking agent> In order to control the molecular weight of the binder resin, a crosslinking agent may be added during polymerization of the polymerizable monomer. As the crosslinking agent, for example, the following compounds can be used, but the crosslinking agent is not limited to these. Ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, and polyester-type diacrylate (MANDA Nippon Kayaku), as well as the above acrylates methacrylated. Something that has been changed to Related. The amount of the crosslinking agent added is preferably 0.001 to 15.0 parts by mass relative to 100.0 parts by mass of the polymerizable monomer.

[0078] <Release agent (wax)> The toner particles may contain a wax. Examples of waxes that can be used include, but are not limited to, the following: Esters of monohydric alcohols and aliphatic monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and aliphatic monoalcohols; Esters of dihydric alcohols and aliphatic monocarboxylic acids, such as dibehenyl sebacate and hexanediol dibehenate, or esters of dihydric carboxylic acids and aliphatic monoalcohols; Esters of trihydric alcohols and aliphatic monocarboxylic acids, such as glycerin tribehenate, or esters of trihydric carboxylic acids and aliphatic monoalcohols; Esters of tetrahydric alcohols and aliphatic monocarboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, or esters of tetrahydric carboxylic acids and aliphatic monoalcohols; Dipentaerythritol hexastenate Examples of suitable waxes include hexavalent alcohols and aliphatic monocarboxylic acid esters such as hexavalent alcohols and dipentaerythritol hexapalmitate, or esters of hexavalent carboxylic acids and aliphatic monoalcohols; polyhydric alcohols and aliphatic monocarboxylic acid esters such as polyglycerin behenate, or esters of polyvalent carboxylic acids and aliphatic monoalcohols; natural ester waxes such as carnauba wax and rice wax; petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and petrolatum; hydrocarbon waxes produced by the Fischer-Tropsch process and derivatives thereof; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid; and acid amide waxes. The wax content in the toner particles is preferably 0.5% by mass to 20.0% by mass.

[0079] <Charge control agent> The toner particles may contain a charge control agent. There are no particular limitations on the charge control agent, and known charge control agents can be used. In particular, charge control agents that have a high charging speed and can stably maintain a constant charge amount are preferred. Furthermore, when the toner particles are produced by a direct polymerization method, charge control agents that have low polymerization inhibition properties and are substantially free of solubilized substances in aqueous media are particularly preferred. Examples of charge control agents that control toner particles to be negatively charged include the following. Organometallic compounds and chelating compounds include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acid and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, or esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, and calixarenes.

[0080] On the other hand, examples of charge control agents that control the toner particles to be positively charged include the following. Nigrosine and nigrosine modifications such as fatty acid metal salts; guanidine compounds; imidazole compounds; onium salts and lake pigments thereof such as quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and their analogous phosphonium salts; triphenylmethane dyes and lake pigments thereof (as a laking agent, phosphonium tungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin-based charge control agents. These charge control agents can be used alone or in combination of two or more. The content of these charge control agents in the toner particles is preferably 0.01% by mass to 10.00% by mass.

[0081] <External additives> The toner particles can be used as a toner without adding any external additives, but in order to improve the fluidity, chargeability, cleaning properties, etc., so-called external additives such as a fluidizing agent and a cleaning aid may be added to the toner. Examples of external additives include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titanium oxide fine particles, inorganic stearic acid compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, and inorganic titanic acid compound fine particles such as strontium titanate and zinc titanate, etc. These may be used alone or in combination of two or more. These inorganic particles are preferably gloss-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, etc. to improve heat-resistant storage properties and environmental stability. The BET specific surface area of ​​the external additive is 10 m 2 / g~450m 2 / g is preferred.

[0082] The BET specific surface area is determined by a low-temperature gas adsorption method using a dynamic constant pressure method in accordance with the BET method (preferably the BET multipoint method). For example, a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas onto the surface of a sample, and the BET multipoint method is used to measure the BET specific surface area (m 2 / g) is calculated. The total amount of these various external additives added is preferably 0.05 to 10.00 parts by mass, more preferably 0.10 to 5.00 parts by mass, relative to 100.00 parts by mass of toner particles. Also, various external additives may be used in combination.

[0083] <Developer> The toner can be used as a magnetic or non-magnetic one-component developer, but may also be mixed with a carrier and used as a two-component developer. The carrier may be magnetic particles made of known materials, such as metals such as iron, ferrite, and magnetite, or alloys of these metals with metals such as aluminum and lead. Among these, ferrite particles are preferred. Alternatively, the carrier may be a coated carrier in which the surfaces of magnetic particles are coated with a coating agent such as resin, or a resin-dispersed carrier in which magnetic powder is dispersed in a binder resin. The carrier preferably has a volume average particle size of 15 μm to 100 μm, more preferably 25 μm to 80 μm.

[0084] <About the manufacturing method of toner particles> Toner particles can be produced by known methods, such as a kneading and pulverization method or a wet production method. From the viewpoint of uniform particle size and shape controllability, a wet production method is preferably used. Further, examples of the wet production method include a suspension polymerization method, a solution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.

[0085] Here, the suspension polymerization method will be described. The suspension polymerization method may include a step of preparing a polymerizable monomer composition by uniformly dissolving or dispersing polymerizable monomers for producing a binder resin, resin A, resin B, a colorant, and other additives as needed, using a disperser such as a ball mill or an ultrasonic disperser (a step of preparing a polymerizable monomer composition). In this case, if necessary, polyfunctional monomers, chain transfer agents, wax as a release agent, charge control agents, plasticizers, etc. may be added appropriately.

[0086] Suitable examples of the polymerizable monomer in the suspension polymerization method include the vinyl polymerizable monomers shown below. Styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-hexylstyrene, p-octylstyrene, p-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, and dibutyl phosphate. acrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

[0087] The suspension polymerization method may include a step (granulation step) of adding the polymerizable monomer composition to a previously prepared aqueous medium and forming droplets of the polymerizable monomer composition into a desired toner particle size using a stirrer or disperser having high shear force. It is preferable that the aqueous medium used in the granulation process contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and prevent the coalescence of toner particles during the manufacturing process. Dispersion stabilizers are generally broadly classified into polymers that exhibit repulsive forces due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive forces. Fine particles of poorly water-soluble inorganic compounds are preferably used because they dissolve in acid or alkali and can be easily removed by washing with acid or alkali after polymerization.

[0088] As the dispersion stabilizer of the poorly water-soluble inorganic compound, one containing any of magnesium, calcium, barium, zinc, aluminum, and phosphorus is preferably used. More preferably, one containing any of magnesium, calcium, aluminum, and phosphorus is used. Specific examples include the following. Sodium phosphate, magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, calcium chloride, hydroxyapatide.

[0089] The dispersion stabilizer may be used in combination with an organic compound such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, or starch. These dispersion stabilizers are used in an amount of 0.01 to 2 parts by mass relative to 100.00 parts by mass of the polymerizable monomer. It is preferred to use 0.00 parts by weight. Furthermore, to further refine these dispersion stabilizers, 0.001 to 0.100 parts by mass of a surfactant may be used in combination with 100.00 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic surfactants, commercially available anionic surfactants, and commercially available cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate, etc. are preferably used.

[0090] The suspension polymerization method may include a step (polymerization step) of obtaining a toner base particle dispersion by polymerizing the polymerizable monomer contained in the polymerizable monomer composition at a temperature preferably set to 50° C. to 90° C. The polymerization step may be carried out after the granulation step or may be carried out while the granulation step is being carried out. In the polymerization step, stirring is preferably performed so as to achieve a uniform temperature distribution in the vessel. When a polymerization initiator is added, it can be added at any timing and for any required time. The temperature may be raised in the latter half of the polymerization reaction in order to obtain a desired molecular weight distribution. Furthermore, in order to remove unreacted polymerizable monomers, by-products, etc. from the system, a portion of the aqueous medium may be distilled off in the latter half of the reaction or after completion of the reaction. The distillation may be performed under normal pressure or reduced pressure.

[0091] In the suspension polymerization method, an oil-soluble initiator is generally used, for example, the following: azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide initiators such as acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide.

[0092] The polymerization initiator may be used in combination with a water-soluble initiator as needed, and examples thereof include the following. Ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyromidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, 2,2'-azobisisobutyronitrile sodium sulfonate, ferrous sulfate, or hydrogen peroxide. These polymerization initiators can be used alone or in combination of two or more. In order to control the degree of polymerization of the polymerizable monomer, it is also possible to use a chain transfer agent, a polymerization inhibitor, etc. in combination.

[0093] The particle size of the toner particles is preferably 3.0 μm to 10.0 μm in weight average particle size in order to obtain high definition and high resolution images. The weight average particle size of the toner can be measured by the capillary electrical resistance method. For example, the Coulter Counter Multisizer The toner particle dispersion thus obtained is sent to a filtration process for solid-liquid separation of the toner particles and the aqueous medium. Solid-liquid separation to obtain toner particles from the obtained toner particle dispersion can be carried out by a general filtration method, and then, in order to remove foreign matter that has not been completely removed from the toner particle surface, it is preferable to further wash the toner particle by reslurrying or washing with washing water. After sufficient washing, solid-liquid separation is again carried out to obtain a toner cake. Thereafter, the toner cake is dried by a known drying means, and if necessary, particle groups having particle sizes other than the specified size are separated by classification to obtain toner particles. The separated particle group having a particle size other than the predetermined particle size may be reused to improve the final yield.

[0094] The methods for measuring the various physical properties are described below. <Method for extracting resin A and resin B from toner particles> Resin A and Resin B in the toner particles are extracted by extracting them with tetrahydrofuran (THF) and separating them by solvent gradient elution. The preparation method is shown below. Weigh out 10.0 g of toner particles, place them in a cylindrical filter paper (Toyo Roshi No. 84), and place them in a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as the solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble fraction. The THF-soluble fraction contains resin A and resin B. Repeat this process multiple times to obtain the required amount of THF-soluble fraction. The solvent gradient elution method uses gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire preparative column 50 mm φ 250 mm). The column temperature is 30 °C, the flow rate is 50 mL / min, and the mobile phase is selected appropriately as good solvents (THF, chloroform, toluene), and as poor solvents (acetonitrile, acetone, methanol, n-hexane). 0.02 g of the THF-soluble fraction was dissolved in 1.5 ml of good solvent and used as a sample for gradient preparative HPLC. The mobile phase started with a 100% poor solvent, and 5 minutes after sample injection, the proportion of good solvent was increased by 4% per minute until the mobile phase was 100% good solvent over 25 minutes. The resulting fractions were dried to obtain Resin A and Resin B. Which fractional section is Resin A can be determined by measuring the silicon atom content, which will be described later, and 13 This can be determined by C-NMR measurement. The required amount of resin A can be obtained by repeating solvent gradient elution as necessary. In addition, which fractional section is resin B will be described later. 1 This can be determined by the presence or absence of a salicylic acid structure using H-NMR measurement. The required amount of resin B can be obtained by repeating solvent gradient elution as necessary.

[0095] <Measurement of Resin A and Resin B Contents in Toner> The resin and resin content in the toner can be calculated from the amounts charged in the toner production. In addition, by identifying and extracting resin A and resin B from each fraction obtained by a method for extracting resin A and resin B from toner particles, the respective contents can be calculated for the toner that has been subjected to a Soxhlet extractor.

[0096] <Method for measuring the content of silicon atoms in resin A> A wavelength dispersive X-ray fluorescence analyzer "Axios" (PANalytical) is used to measure the content of silicon atoms in Resin A. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "SuperQ ver. 4.0F" (PANalytical). The anode of the X-ray tube is Rh, and the acceleration voltage and current are 24 kV and 100 mA, respectively. The measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. A proportional counter (PC) is used as the detector. The measurement is performed by measuring the count rate (unit: cps) of Si-Kα rays observed at a diffraction angle (2θ) = 109.08° when PET is used as the analyzing crystal, and calculating using the following calibration curve. The measurement sample is either the synthesized resin A or the resin A extracted from the toner particles by the above-described extraction method. The pellets for measurement are made using a tablet molding and compression machine "BRE-32" (manufactured by Maekawa Testing Machinery Manufacturing Co., Ltd.) 4 g of the measurement sample is placed in a special aluminum ring for pressing, flattened, and pressed at 20 MPa for 60 seconds to form pellets with a thickness of 2 mm and a diameter of 39 mm. As pellets to create a calibration curve for determining the content, binder [product name: Spectro Blend, Ingredients: C 81.0, O 2.9, H 13.5, N 2.6 (mass%), Chemical formula: C 19 H 38 SiO2 (hydrophobic fumed silica) [product name: AEROSIL NAX50, specific surface area: 40±10 m] per 100 parts by mass of SiO2 (hydrophobic fumed silica) [product name: AEROSIL NAX50, specific surface area: 40±10 m] 2 0.50 parts by mass of SiO2 (0.00 parts by mass, 0.45% to 0.85% carbon content; manufactured by Nippon Aerosil Co., Ltd.) was added, thoroughly mixed using a coffee mill, and molded into pellets. Similarly, SiO2 was added to the mixture so that the amounts were 5.00 parts by mass, 10.00 parts by mass, and 15.00 parts by mass, and then molded into pellets. A linear calibration curve is obtained by plotting the count rate of the obtained X-rays on the vertical axis and the concentration of Si added in each calibration sample on the horizontal axis. Next, the count rate of Si-Kα rays is measured for the measurement sample in the same manner, and the silicon atom content (mass %) is determined from the obtained calibration curve.

[0097] <Confirmation of the structure of resin A represented by formula (1) (R 1 ~R 3 )> R in resin A represented by formula (1) 1 ~R 3 The structure of 29 Si-NMR (solid state) measurement, and 13 The measurement conditions are as follows: The measurement sample is either the synthesized resin A or the resin A extracted from the toner particles by the above-mentioned extraction method. ( 29 Si-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2 mm diameter Sample amount: 150 mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 97.38MHz ( 29 Si) Reference material: DSS (external standard: 1.534ppm) Sample rotation speed: 10kHz Contact time: 10ms Delay time: 2 seconds Accumulation times: 2000 to 8000 times The above measurement allows the abundance ratio of multiple silane components according to the number of oxygen atoms bonded to silicon to be determined by peak separation and integration using curve fitting, thereby confirming the structure of R1 to R3 of the resin represented by formula (1).

[0098] (13C-NMR (solid state) measurement conditions) Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2 mm diameter Sample amount: 150 mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz (13C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2 seconds Number of times accumulated: 1024 By the above measurement, various peaks are separated depending on the types of R1 to R3 in formula (1), and each peak is identified to determine the structures of R1 to R3.

[0099] <Confirmation of the structure of resin A represented by formula (1) (P1 and L1)> The structures of P1 and L1 in the resin represented by formula (1) can be confirmed by C-NMR (solid) measurement. The measurement conditions are the same as those described above (C-NMR (solid) measurement conditions). The measurement sample used is synthesized resin A or resin A extracted from toner particles by the extraction method described above. By the above measurement, various peaks are separated depending on the types of P1 and L1 in formula (1), and each is identified to determine the structures of P1 and L1.

[0100] <Confirming the structure of Resin B> The structure of Resin B was determined using nuclear magnetic resonance spectroscopy (1H-NMR) [400 MHz, CDCl3, room temperature (25°C)]. 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 The molar ratio of each monomer component is determined from the integral value of the obtained spectrum, and the structure of resin B and the mol % of the monovalent group having salicylic acid contained in resin B are calculated based on this.

[0101] <Confirming the structure of colorants> The separation of the colorant contained in the toner and confirmation of its structure are carried out as follows. 50g of toner is placed in a 1L beaker containing 500g of THF and stirred at 100 rpm using a magnetic stirrer for 24 hours. The resulting dispersion is left to stand for 24 hours to allow the insoluble matter to settle. The THF-soluble matter (supernatant) containing the colorant dispersion is then recovered by decantation. The recovered supernatant is centrifuged to recover the settled colorant. The recovered colorant is washed three times with distilled water, dried, and then the aggregated coarse particles are crushed in a mortar. If the amount of colorant required for measurement is not reached, the above procedure is repeated. The resulting colorant is then subjected to pyrolysis GC / MS measurement.

[0102] <Measurement conditions for pyrolysis GC / MS> Pyrolysis equipment: Japan Analytical Industry Co., Ltd. TPS-700 Thermal decomposition temperature: Optimum value between 400℃ and 600℃ GC / MS equipment: ISQ manufactured by Thermo Fisher Scientific Co., Ltd. Column: "HP5-MS" (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm GC / MS conditions Filler requirements: InletTemp: 250℃, Split Flow: 50ml / min GC temperature rise conditions: 40°C (5 min) → 10°C / min (300°C) → 300°C (20 min) Mass range: m / z = 10 to 550

[0103] <Method for measuring weight average molecular weight (Mw)> The weight average molecular weight (Mw) of a resin or the like is measured by gel permeation chromatography (GPC) as follows. First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used for measurements under the following conditions. Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL To calculate the molecular weight of the sample, a molecular weight calibration curve prepared using standard polystyrene resins (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) was used.

[0104] <Method for measuring the acid value Av of a resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of a resin is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure. (1) Preparation of reagents Dissolve 1 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., and leave for 3 days. Then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998. (2) Operation (A) Main test 2.0 g of the crushed sample was accurately weighed into a 200 ml Erlenmeyer flask, and 100 ml of a toluene / ethanol (2:1) mixture was added and allowed to dissolve for 5 hours. Next, a few drops of the phenolphthalein solution were added as an indicator, and the sample was titrated with the potassium hydroxide solution. The endpoint of the titration was when the indicator's light red color persisted for approximately 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used). (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added in the blank test (ml), C is the amount of potassium hydroxide solution added in the main test (ml), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0105] <Method for measuring the hydroxyl value (OHv) of a resin> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl groups when acetylating 1 g of a sample. The hydroxyl value of a resin is measured in accordance with JIS K 0070-1992, specifically, according to the following procedure. (1) Preparation of reagents Place 25 g of special-grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in an amber bottle to avoid contact with moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 35 g of special-grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., and leave for 3 days. Then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. 0.5 mol / L hydrochloric acid prepared in accordance with JIS K 8001-1998 is used. (2) Operation (A) Main test Accurately weigh 1.0 g of the ground sample into a 200 mL round-bottom flask, and add 5.0 mL of the acetylation reagent using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special-grade toluene to dissolve it. Place a small funnel on the neck of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97°C. To prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is recommended to cover the base of the neck of the flask with a piece of cardboard with a round hole. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After allowing it to cool, add 1 mL of water through the funnel and shake to hydrolyze the acetic anhydride. To further complete the hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After allowing it to cool, wash the funnel and the walls of the flask with 5 mL of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The endpoint of the titration is when the light red color of the indicator lasts for about 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used. (3) The obtained results are substituted into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D where A is the hydroxyl value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, S is the mass of the sample (g), and D is the acid value of the sample (mgKOH / g). [Example]

[0106] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples. Unless otherwise specified, the "parts" and "%" of each material in the examples and comparative examples are all based on mass.

[0107] <Production example of styrene acrylic resin (R-1)> A styrene-acrylic resin (R-1) was produced according to the following procedure. 100.0 parts of propylene glycol monomethyl ether was heated while purging with nitrogen and refluxed at a liquid temperature of 120° C. or higher. A mixture of 83.4 parts of styrene, 20.9 parts of butyl acrylate, and 1.0 part of acrylic acid as polymerizable monomers, and 0.6 parts of tert-butyl peroxybenzoate (manufactured by NOF Corporation, trade name: Perbutyl Z) as a polymerization initiator was added dropwise thereto over 3 hours. After the dropwise addition was completed, the solution was stirred for 3 hours and then distilled at atmospheric pressure while increasing the liquid temperature to 170°C. After the liquid temperature reached 170°C, the pressure was reduced to 1 hPa, and distillation was continued for 1 hour to remove the solvent, yielding a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain a styrene acrylic resin (R-1). The resulting styrene acrylic resin (R-1) had an acid value of 10.6 mgKOH / g and a weight average molecular weight (Mw) of 13,000.

[0108] <Production example of styrene acrylic resin (R-2)> In the production example of styrene-acrylic resin (R-1), the polymerizable monomers were changed to 82.0 parts of styrene, 10.0 parts of methacrylic acid, and 8.0 parts of acrylic acid, and the amount of the polymerization initiator was changed to 0.2 parts, respectively. A styrene-acrylic resin (R-2) was obtained by the same procedure. The resulting styrene acrylic resin (R-2) had an acid value of 161.0 mgKOH / g and a weight average molecular weight (Mw) of 46,000.

[0109] <Production example of polyester resin (R-3)> A polyester resin (R-3) was produced according to the following procedure. The following materials were charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and the reaction was carried out under a nitrogen atmosphere at normal pressure and 200°C for 5 hours. Bisphenol A-propylene oxide 2.1 mole adduct: 39.6 parts Terephthalic acid: 8.0 parts Isophthalic acid: 7.6 parts Tetrabutoxytitanate: 0.1 parts Thereafter, 0.01 parts of trimellitic acid and 0.12 parts of tetrabutoxy titanate were added, and the mixture was reacted at 220° C. for 3 hours, and then further reacted under reduced pressure of 10 mmHg to 20 mmHg for 2 hours to obtain a polyester resin (R-3). The resulting polyester resin (R-3) had an acid value of 6.1 mgKOH / g and a weight average molecular weight (Mw) of 10,200.

[0110] <Production Examples of Polyester Resins (R-4), (R-5), and (R-9)> In the production example of polyester resin (R-3), polyester resins (R-4), (R-5) and (R-9) were produced in the same manner except that the reaction pressure, reaction temperature and reaction time were appropriately adjusted in order to obtain a lower molecular weight material or a higher molecular weight material. The resulting polyester resin (R-4) had an acid value of 28.0 mgKOH / g and a weight average molecular weight (Mw) of 3,100. The acid value of the obtained polyester resin (R-5) was 1.2 mgKOH / g and the weight average molecular weight (Mw) was 99,500. The resulting polyester resin (R-9) had an acid value of 30.9 mgKOH / g and a weight average molecular weight (Mw) of 1,800.

[0111] <Synthesis of acrylic resin (R-6)> An acrylic resin (R-6) was synthesized as follows. 100.0 parts of propylene glycol monomethyl ether was heated while purging with nitrogen and refluxed at a liquid temperature of 120° C. or higher. A mixture of 30.0 parts of methyl methacrylate, 50.4 parts of acrylic acid, and 1.0 part of tert-butyl peroxybenzoate (organic peroxide polymerization initiator, manufactured by NOF Corporation, trade name: Perbutyl Z) was added dropwise thereto over 3 hours. After the dropwise addition was completed, the solution was stirred for 3 hours and then distilled at atmospheric pressure while increasing the liquid temperature to 170°C. After the liquid temperature reached 170°C, the pressure was reduced to 1 hPa, and distillation was continued for 1 hour to remove the solvent, yielding a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain acrylic resin (R-6). The acid value of the resulting acrylic resin (R-6) was 351.8 mgKOH / g and Mw=8700.

[0112] <Synthesis of polyester resin (R-7)> Poly-ε-caprolactone with stearyl ester at the carboxylic acid end was prepared by the following procedure. Polyester resin (R-7) was synthesized. The following materials were placed in a reaction vessel equipped with a nitrogen gas inlet, a temperature measuring device, and a stirrer, and the reaction was carried out at 100°C for 5 hours under a nitrogen atmosphere. Stearyl alcohol: 3.0 parts ε-caprolactone: 38.2 parts Titanium(IV) tetraisopropoxide: 0.5 parts The obtained resin was dissolved in chloroform, and the solution was added dropwise to methanol for reprecipitation and filtration to obtain polyester (R-7). The resulting polyester resin (R-7) had an acid value of 0.0 mgKOH / g, a hydroxyl value of 30.3 mgKOH / g, and Mw=8,300.

[0113] <Synthesis of polyester resin (R-8)> Polylactic acid [(polyester resin (R-8)]] was synthesized according to the following procedure. The following materials were charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and the reaction was carried out under a nitrogen atmosphere at atmospheric pressure and 200°C for 5 hours. Lactic acid: 100.0 parts Tetrabutoxytitanate: 0.1 parts Then, 0.1 parts of tetrabutoxy titanate was added, and the mixture was reacted at 220°C for 3 hours, and then further reacted for 2 hours under reduced pressure of 10 mmHg to 20 mmHg. The obtained resin was dissolved in chloroform, and the solution was added dropwise to ethanol for reprecipitation and filtration to obtain polyester resin (R-8). The resulting polyester resin (R-8) had an acid value of 3.5 mgKOH / g and Mw=30,000.

[0114] <Production example of resin A> <Production example of resin (A-1)> Resin (A-1) represented by formula (1) was produced by the following procedure. 50.00 parts of styrene acrylic resin (R-1) was dissolved in 200.00 parts of N,N-dimethylacetamide, and 1.20 parts of 3-aminopropyltriethoxysilane and 2.87 parts of triethylamine were added as silane compounds, and 2.88 parts of DMT-MM [4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride] was added as a condensing agent, followed by stirring at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol to cause reprecipitation and filtration, yielding resin (A-1). The weight average molecular weight Mw of resin (A-1) was 13,200.

[0115] <Production Examples of Resins (A-2) to (A-8), (A-10), (A-11), (A-13), (A-14), (A-16) to (A-18)> In the production example of resin (A-1), P 1 Resins (A-2) to (A-8), (A-10), (A-11), (A-13), (A-14), and (A-16) to (A-18) were obtained in the same manner, except that the type of (polymer moiety); the type and amount of silane compound added; and the amount of triethylamine and DMT-MM added were changed as shown in Table 1.

[0116] <Production example of resin (A-9)> A solution of 10.0 parts of resin (A-8) dissolved in 90.0 parts of toluene was mixed with 400.0 parts of pure water and stirred, the pH was adjusted to 4.0 using dilute hydrochloric acid, and the mixture was stirred at room temperature for 10.8 hours. After that, the stirring was stopped and the mixture was transferred to a separatory funnel to extract the oil phase. The oil phase was concentrated and reprecipitated with methanol to obtain resin (A-9) represented by formula (1). The obtained resin (A-9) 29 Analysis by Si-NMR (solid state) measurement revealed that R 1 ~R 3 were all hydroxy groups.

[0117] <Production example of resin (A-12)> Resin (A-12) was produced according to the following procedure. 50.00 parts of polyester resin (R-3) was dissolved in 500.00 parts of chloroform, and 0.74 parts of 3-isocyanatepropyltriethoxysilane and 0.50 parts of titanium (IV) tetraisopropoxide were added under a nitrogen atmosphere and stirred at room temperature for 5 hours. After the reaction was completed, the solution was dropped into methanol, reprecipitated, and filtered to obtain resin (A-12).

[0118] <Production example of resin (A-15)> Resin (A-15) was synthesized in the same manner as in the synthesis of Resin (A-12), except that Polyester (R-3) was changed to Polyester (R-7) and the amount of 3-isocyanatepropyltriethoxysilane added was changed from 0.74 parts to 6.61 parts.

[0119] <Production example of resin (A-19)> Diphenylmethane diisocyanate (MDI) 41.3 parts Bisphenol A ethylene oxide 2 mole adduct (BPA-2EO) 33.8 parts Tetrahydrofuran (THF) 300.0 parts The above mixture was placed in a reaction vessel equipped with a stirrer and a thermometer while the atmosphere was replaced with nitrogen. The mixture was heated to 50°C and subjected to a urethane reaction for 8 hours. 1.0 part of ethoxysilane was added and the reaction was continued for another 8 hours, and then 3.0 parts of t-butyl alcohol was added to modify the isocyanate terminal. The solvent THF was distilled off to obtain resin (A-19).

[0120] [Table 1] Table 2 shows the physical properties of the resulting resins (A-1) to (A-19).

[0121] [Table 2] In the table, the silicon concentration indicates the content of silicon atoms in resin A.

[0122] <Resin B manufacturing example> <Synthesis example of polymerizable monomer M-1> 18.0 g of 2,4-dihydroxybenzoic acid was dissolved in 150 mL of methanol, and 36.9 g of potassium carbonate was added and heated to 65° C. A mixture of 18.7 g of 4-(chloromethyl)styrene and 100 mL of methanol was added dropwise to the reaction solution, and the reaction was carried out at 65° C. for 3 hours. After cooling the reaction solution, it was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1.5 L of water at pH 2, and extracted with ethyl acetate. The mixture was then washed with water, dried over magnesium sulfate, and the ethyl acetate was removed under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain 20.1 g of polymerizable monomer M-1, represented by the following structural formula (21).

[0123] [ka]

[0124] <Synthesis example of polymerizable monomer M-2> 100 g of 2,5-dihydroxybenzoic acid and 1,441 g of 80% sulfuric acid were mixed and heated to 50° C. 144 g of tert-butyl alcohol was added to this dispersion and stirred for 30 minutes at 50° C. Then, 144 g of tert-butyl alcohol was added to this dispersion and stirred for 30 minutes, and this operation was repeated three times. The reaction mixture was cooled to room temperature and slowly poured into 1 kg of ice water. The precipitate was filtered and washed with water. The precipitate was then washed with hexane. The precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, the mixture was dried at 80°C to obtain 74.9 g of a salicylic acid intermediate represented by the following structural formula (22).

[0125] [ka]

[0126] 20.1 g of polymerizable monomer M-2 represented by the following structural formula (23) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 18.0 g of 2,4-dihydroxybenzoic acid was changed to 25.0 g of the salicylic acid intermediate represented by the structural formula (22).

[0127] [ka]

[0128] <Synthesis example of polymerizable monomer M-3> A salicylic acid intermediate was obtained in the same manner as in the synthesis of polymerizable monomer M-2, except that 144 g of tert-butyl alcohol was replaced with 253 g of 2-octanol. A polymerizable monomer M-3 of the following structural formula (24) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 32 g of the salicylic acid intermediate obtained here was used.

[0129] [ka]

[0130] <Synthesis example of polymerizable monomer M-4> Polymerizable monomer M-4 of the following structural formula (25) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 18.0 g of 2,4-dihydroxybenzoic acid was changed to 18 g of 2,3-dihydroxybenzoic acid.

[0131] [ka]

[0132] <Synthesis example of polymerizable monomer M-5> Polymerizable monomer M-5 of the following structural formula (26) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 18.0 g of 2,4-dihydroxybenzoic acid was changed to 18 g of 2,6-dihydroxybenzoic acid.

[0133] [ka]

[0134] <Synthesis example of polymerizable monomer M-6> Polymerizable monomer M-6 of the following structural formula (27) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 18.0 g of 2,4-dihydroxybenzoic acid was changed to 18 g of 2,5-dihydroxy-3-methoxybenzoic acid.

[0135] [ka] Me represents a methyl group.

[0136] <Synthesis example of resin (B-1)> Polymerizable monomer M-1 (7.6 g) represented by structural formula (21), styrene (46.9 g), and 2-ethylhexyl acrylate (15.5 g) were dissolved in 42.0 ml of DMF, stirred for 1 hour while bubbling with nitrogen, and then heated to 110°C. To this reaction solution, a mixture of 42 ml of toluene and 2.1 g of tert-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name Perbutyl I) was added dropwise as an initiator. The reaction was continued at 110°C for another 4 hours. The mixture was then cooled and added dropwise to 1 L of methanol to obtain a precipitate. The resulting precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to deposit a white precipitate, which was then filtered and dried at 90 ° C under reduced pressure to obtain polymer B-1 (66.5 g). The NMR and acid value of the resulting resin (B-1) were measured to confirm the content of components derived from polymer monomer M-1.

[0137] <Synthesis Examples of Resins (B-2) to (B-10), (B-12), and (B-13)> Resins (B-2) to (B-10), (B-12), and (B-13) were obtained in the same manner as in the synthesis example of resin (B-1), except that the amounts of raw materials charged were changed as shown in Table 3. In Table 3, St represents styrene, 2EHA represents 2-ethylhexyl acrylate, and BA represents butyl acrylate.

[0138] <Synthesis example of resin (B-11)> Polymerizable monomer M-7 represented by the following chemical formula (28) was obtained in the same manner as in the synthesis example of polymerizable monomer M-1, except that 2,4-dihydroxybenzoic acid was changed to 2,5-dihydroxybenzoic acid and 4-(chloromethyl)styrene was changed to p-aminobenzyl chloride. Bisphenol A propylene oxide 2.2 mole adduct 67.8 parts Terephthalic acid 22.2 parts Trimellitic anhydride 10.0 parts Dibutyltin oxide 0.00500 parts Next, the above materials were placed in a four-necked flask, and a thermometer, a stirring rod, a condenser, and a nitrogen inlet tube were attached, and the mixture was reacted at 220° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin P-1. A reaction vessel was charged with 85.0 parts of the obtained polyester resin P-1 and 15.0 parts of the polymerizable monomer M-7 represented by the following formula (28), and a condenser, stirrer, and thermometer were immersed. 270 parts of pyridine were added and stirred, and then 96.0 parts of triphenyl phosphite was added and stirred at 120°C for 6 hours. After the reaction was completed, the mixture was reprecipitated in 360 parts of ethanol and recovered. The obtained polymer was washed twice with 140 parts of 1 mol / L hydrochloric acid, then washed twice with 140 parts of water, and dried under reduced pressure to obtain a resin (B-11).

[0139] [ka]

[0140] <Synthesis example of resin (B-14)> Diphenylmethane diisocyanate (MDI) 41.3 parts Bisphenol A ethylene oxide 2 mole adduct (BPA-2EO) 33.8 parts 2-Hydroxy-4-isocyanatobenzoic acid 10.0 parts Tetrahydrofuran (THF) 300.0 parts The above mixture was placed in a reaction vessel equipped with a stirrer and a thermometer while the atmosphere was replaced with nitrogen. The mixture was heated to 50°C and subjected to a urethane reaction for 15 hours. 3.0 parts by mass of t-butyl alcohol was then added to modify the isocyanate terminals. The solvent, THF, was distilled off to obtain Resin (B-14).

[0141] [Table 3]

[0142] <Production Example of Toner Particle 1> 390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) (manufactured by Rasa Kogyo Co., Ltd.) were added to a reaction vessel, and the mixture was kept at 65°C for 1.0 hour while purging with nitrogen. Next, the mixture was mixed at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While stirring at 50°C, an aqueous calcium chloride solution prepared by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water was added all at once to prepare an aqueous medium containing a dispersion stabilizer. Further, hydrochloric acid was added to the aqueous medium to adjust the pH to 6.0, thereby obtaining aqueous medium 1. Separately, the following materials were placed in an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and then zirconia particles with a diameter of 1.7 mm were added. The mixture was dispersed at 220 rpm for 5.0 hours, after which the zirconia particles were removed to prepare Dispersion 1 in which the colorant was dispersed. Styrene 60.0 parts Colorant (CI Pigment Yellow 155) 6.5 parts Next, the following materials were added to the prepared dispersion 1. Styrene 15.0 parts 25.0 parts n-butyl acrylate Polyester resin (R-3) 4.0 parts Resin A (A-1) 1.0 parts ·Resin B (B-1) 1.0 part Divinylbenzene 0.3 parts Wax (Fischer-Tropsch wax, melting point: 78°C) 9.0 parts The mixture was kept at 65° C. and uniformly dissolved and dispersed using a TK homomixer at 500 rpm to prepare a polymerizable monomer composition 1. While maintaining the temperature of the aqueous medium 1 at 70°C and the rotation speed of the stirrer at 12,000 rpm, the polymerizable monomer composition 1 was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate was added as a polymerization initiator. Granulation was continued for 10 minutes while maintaining the stirring speed at 12,000 rpm with the stirrer. The stirring device was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 150 rpm and maintaining the temperature at 70°C. The temperature was then raised to 85°C and maintained at this temperature for 2.0 hours, and the mixture was then cooled to room temperature, thereby obtaining toner particle dispersion 1. Hydrochloric acid was added to the obtained toner particle dispersion liquid 1 to adjust the pH to 1.4 or less, and the dispersion stabilizer was dissolved therein. The resulting mixture was filtered, washed, and dried to obtain toner particles 1.

[0143] <Production Examples of Toner Particles 2 to 23, 25 to 40, and 46 to 50> Toner particles 2 to 23, 25 to 40, and 46 to 50 were produced in the same manner as in the production example of toner particles 1, except that dispersion liquid 1 and the materials added to dispersion liquid 1 were changed as shown in Table 4.

[0144] [Table 4] In the table, PY represents CI Pigment Yellow and PR represents CI Pigment Red.

[0145] <Production Example of Toner Particles 24> (Production of polyester resin 1) Monomers in the amounts shown in Table 5 were placed in a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and then 1.5 parts of dibutyltin as a catalyst per 100 parts of the total amount of monomers was added. Next, the temperature was quickly raised to 180°C under normal pressure in a nitrogen atmosphere, and then polycondensation was carried out by distilling off water while heating from 180°C to 210°C at a rate of 10°C / hour. After the temperature reached 210°C, the pressure inside the reaction vessel was reduced to 5 kPa or less, and polycondensation was carried out under conditions of a temperature of 210°C and 5 kPa or less, to obtain polyester resin C. At that time, the polymerization time was adjusted so that the softening point of the resulting polyester resin C would be 115°C.

[0146] [Table 5] TPA stands for terephthalic acid, and BPA-PO stands for bisphenol A-propylene oxide 2-mol adduct.

[0147] Polyester resin C 90.0 parts Polyester resin (R-3) 10.0 parts CI Pigment Yellow 74 7.0 parts Resin A (A-3) 2.0 parts ·Resin B (B-1) 2.0 parts Paraffin wax (DSC peak temperature: 80°C) 5.0 parts The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.), and then mixed in a twin-screw mixer (PCM-30 model, manufactured by Ikegai Iron Works Co., Ltd.) at a rotation speed of 3.3 s. -1 The mixture was kneaded at a kneading temperature of 120°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.). The finely pulverized powder was further classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 24 having a weight average particle size of 7.0 μm.

[0148] <Production Example of Toner Particles 41> (Production of dispersion of binder resin particles) 60 g of ethylene vinyl acetate resin (Ultrathene 685, manufactured by Tosoh) was added to 200 g of toluene (manufactured by Wako Pure Chemical Industries), heated to 90°C, and then stirred for 3 hours to dissolve. 180 g of ion-exchanged water containing 6 g of anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku) and 3 g of anionic surfactant (NonSal LN1, manufactured by Nippon Oil & Fats) was added to the toluene solution containing the ethylene vinyl acetate resin. The mixture was then thoroughly stirred at 4000 rpm using an ultra-high speed stirring device, TK Robomix (manufactured by Primix Corporation), and then dispersed for about 1 hour using a high-pressure impact disperser, Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), after which the toluene was removed using an evaporator to obtain a dispersion of binder resin fine particles.

[0149] (Production of Dispersion of Resin A (A-1)) A dispersion of resin A (A-1) was obtained in the same manner as in the preparation of the dispersion of binder resin particles, except that ethylene vinyl acetate resin was replaced with resin A (A-1).

[0150] (Production of Dispersion of Resin B (B-1)) A dispersion of resin B (B-1) was obtained in the same manner as in the preparation of the dispersion of binder resin particles, except that ethylene vinyl acetate resin was replaced with resin B (B-1).

[0151] (Production of dispersion of release agent particles) Release agent (HNP-51, melting point 78°C, manufactured by Nippon Seiro) 20.0 parts Anionic surfactant (Dai-ichi Kogyo Seiyaku: Neogen RK) 1.0 part 79.0 parts ion-exchanged water The above formulation was placed in a mixing vessel equipped with a stirrer, heated to 90°C, and circulated through a Clearmix W Motion (manufactured by M Technique) where it was stirred at a shear stirring location with a rotor outer diameter of 3 cm and a clearance of 0.3 mm at a rotor rotation speed of 19,000 r / min and a screen rotation speed of 19,000 r / min, and dispersed for 60 minutes. After that, it was cooled to 40°C under cooling conditions of a rotor rotation speed of 1,000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min, to obtain a dispersion of release agent microparticles.

[0152] (Production of pigment dispersion) ·CIPigment Yellow 74: 10.0 copies Ion-exchanged water: 78.0 parts Anionic surfactant (Dai-ichi Kogyo Seiyaku: Neogen RK): 2.0 parts The above materials were mixed and then dispersed for 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to prepare a pigment dispersion.

[0153] 320.0 parts binder resin particle dispersion (solid content 25%) Pigment dispersion (solid content 10%) 50.0 parts 50.0 parts of dispersion of release agent particles (20% solids) 2.0 parts of dispersion of resin A (A-1) (solid content 25%) 8.0 parts of dispersion of resin B (B-1) (solid content 25%) The above materials were placed in a round stainless steel flask and mixed. An aqueous solution of 8 parts magnesium sulfate dissolved in 98 parts ion-exchanged water was added to the flask, and the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer (IKA Ultra Turrax T50). The mixture was then heated to 50°C in a heated water bath using a stirring blade while appropriately adjusting the rotation speed so that the mixture was stirred. After holding at 50°C for 1 hour, the weight-average particle diameter of the formed aggregated particles was measured. The results confirmed that aggregated particles with a weight-average particle diameter of approximately 6.0 μm had been formed. To the resulting dispersion of aggregated particles, an aqueous solution of 40 parts of sodium ethylenediaminetetraacetate dissolved in 360 parts of ion-exchanged water was added, followed by 2,800 parts of ion-exchanged water. The mixture was heated to 80°C while continuing to stir and held in a sealed state for 2 hours to obtain fully fused particles. After filtration and solid-liquid separation, the filter cake was thoroughly washed with ion-exchanged water and dried in a vacuum dryer to obtain toner particles 41 with a weight average particle diameter of 5.6 μm.

[0154] <Production Example of Toner Particles 42> Aqueous medium 2 was prepared by mixing 660.0 parts of ion-exchanged water and 25.0 parts of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate and stirring the mixture at 10,000 rpm using a TK homomixer. The following materials were added to 500.0 parts of ethyl acetate and dissolved at 100 rpm using a propeller stirrer to prepare a solution. Styrene / butyl acrylate copolymer 100.0 parts (Copolymerization mass ratio: 80 / 20) Resin A (A-1) 4.0 parts ·Resin B (B-1) 0.8 part Polyester resin (R-1) 5.0 parts Colorant (CI Pigment Yellow 155) 6.5 parts Fischer-Tropsch wax (melting point: 78°C) 9.0 parts 150.0 parts of aqueous medium 2 was placed in a container and stirred at 12,000 rpm using a TK homomixer, and 100.0 parts of the solution was added thereto and mixed for 10 minutes to prepare an emulsified slurry. Then, 100.0 parts of the emulsified slurry was placed in a flask equipped with a degassing pipe, a stirrer, and a thermometer, and the solvent was removed under reduced pressure at 30°C for 12 hours while stirring at 500 rpm, and the mixture was aged at 45°C for 4 hours to obtain a solvent-free slurry. The solvent-removed slurry was filtered under reduced pressure, and then 300.0 parts of ion-exchanged water was added to the resulting filter cake, which was mixed and re-dispersed in a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. The obtained filter cake was dried in a dryer at 45° C. for 48 hours and sieved through a mesh with an opening of 75 μm to obtain toner particles 42.

[0155] <Production Example of Toner Particles 43> Toner particles 43 were obtained in the same manner as in the production example of toner particles 24, except that resin B (B-1) in the production example of toner particles 24 was changed to resin B (B-11).

[0156] <Production Example of Toner Particles 44> In the manufacturing example of toner particle 24, toner particle 44 was obtained in the same manner as toner particle 24, except that polyester resin C was changed to styrene / butyl acrylate copolymer (copolymerization mass ratio: 80 / 20) and resin A (A-3) was changed to resin A (A-1).

[0157] <Production Example of Toner Particle 45> Toner particles 45 were obtained in the same manner as in the manufacturing example of toner particles 41, except that resin A (A-1) was changed to resin A (A-3) and resin B (B-1) was changed to resin B (B-11).

[0158] <Toner 1-50 manufacturing example> For 100.0 parts of each of the obtained toner particles 1 to 50, the BET value was 200 m 2 / g and 0.6 parts of hydrophobic silica fine particles having a number average particle size of primary particles of 8 nm were mixed in a Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.). After the above-mentioned mixing treatment, the mixture was sieved through a mesh with an opening of 150 μm to obtain toners 1 to 50. The physical properties of the obtained toners 1 to 50 are shown in Table 6.

[0159] [Table 6]

[0160] [Examples 1 to 44, Comparative Examples 1 to 6] The methods for evaluating each of Toners 1 to 50 are described below, and the evaluation results are shown in Tables 7-1 and 7-2. Examples 1 to 6, 8, 13, 23 to 40, 42, and 44 were evaluated as reference examples. The image forming device is a commercially available laser printer, HPColor LaserJ. A modified HP Enterprise CP4525dn was used. The modifications to this evaluation machine are as follows: (1) The process speed was increased to 300 mm / sec by changing the gear and software of the evaluation machine. (2) The cartridge used for evaluation was a yellow cartridge. That is, the product toner was removed from a commercially available yellow cartridge, the inside was cleaned with an air blower, and then 220 g of the toner to be evaluated was filled and evaluated. Note that the product toner was removed from each of the cyan, magenta, and black stations, and cyan, magenta, and black cartridges with the remaining toner detection mechanism disabled were inserted.

[0161] [Coloring power] Canon Color Laser Copier Paper (A4 size, 81.4 g / m 2 , manufactured by Canon) with a toner loading of 0.40 (mg / cm 2 ) was output at a fixing temperature of 190°C and a process speed of 300 mm / sec. The image density of the image was measured using an X-Rite color reflection densitometer, and then the coloring strength was evaluated based on the following evaluation criteria. A: Image density is 1.40 or more B: Image density is 1.20 or more and less than 1.40 C: Image density is less than 1.20

[0162] [Light resistance] The color strength measurements and their a * , b * was measured using "Spectrolino" (manufactured by Gretag Macbeth), and this result was used as the initial value. , the image was measured at intensity 8 in a Super Fluorescent Lamp Fade Meter FL (manufactured by Suga Test Instruments Co., Ltd.) 0000 (lux) light was irradiated for 360 hours in a normal temperature and humidity environment (23°C / 60%RH), and the a * , b * The color difference (ΔE) from the initial value was calculated. After that, the intensity was measured in a Super Fluorescent Lamp Fade Meter FL (manufactured by Suga Test Instruments Co., Ltd.). Irradiated with 80,000 lux light for 360 hours. * , b * was measured and the color difference (ΔE) from the initial value was calculated. A test was also conducted in a high temperature and humidity environment (30°C / 85%RH) where light of 80,000 lux intensity was irradiated for 720 hours. * , b * was measured and the color difference (ΔE) from the initial value was calculated. The light resistance was evaluated based on the following evaluation criteria. A: ΔE is less than 3.0 B: ΔE is 3.0 or more and less than 5.0 C: ΔE is 5.0 or more and less than 8.0 D: ΔE is 8.0 or more and less than 10.0 E: ΔE is 10.0 or more and less than 13.0 F: ΔE is 13.0 or more

[0163] [Toner cracking] The durability of the toner against cracking was evaluated as follows. A durability test was conducted using the same image forming device as above under a low temperature and low humidity environment (temperature 15°C, relative humidity 10%) with a print rate of 0.0%, and a solid image was output every 1000 sheets. Subsequently, streaky images due to poor development caused by cracked toner or missing toner were evaluated according to the following criteria depending on the number of sheets on which such images occurred. Here, streaky images due to poor development are determined by observing the toner and developing blade in the cartridge at the time when streaks appear on the image. This corresponds to the case where cracked or chipped toner is present in the cartridge and furthermore, such toner is confirmed to be fused to the developing blade. The toner and developing blade were observed at 1000x magnification using a scanning electron microscope (SEM). (Evaluation criteria) A: The number of occurrences is 20,000 or more. B: The number of occurrences is between 15,000 and 20,000. C: The number of occurrences is between 10,000 and 15,000. D: The number of occurrences is between 5,000 and 10,000. E: Number of occurrences is less than 5,000

[0164] [Charging property] <Evaluation of Toner Charging Amount> A two-component developer was prepared as follows. To evaluate the charge amount, a sample was prepared as follows: 37.2 g of magnetic carrier F813-300 (manufactured by Powder Tech Co., Ltd.) and 2.8 g of the toner to be evaluated were placed in a 100 mL plastic bottle with a lid, and the bottle was shaken for 1 minute at a speed of 150 rpm using a shaker (YS-LD: manufactured by Yayoi Co., Ltd.). The toner and the two-component developer were evaluated as follows. To measure the charge amount, 20 g of the two-component developer was taken and left under condition 1 [5 days and nights in a high-temperature, high-humidity environment (30°C / 85% RH)] and condition 2 [5 days and nights in a normal temperature, normal humidity environment (23°C / 60% RH)], after which it was placed in a 50 cc insulating plastic container and shaken at a speed of 150 rpm for 7 minutes, and measured using the device shown in Figure 1. In addition, 20 g of two-component developer was also left under condition 3 [30 days in a harsh environment (40°C / 95% RH) and then another day and night in a high-temperature, high-humidity environment (30°C / 85% RH)] and evaluated in the same way.

[0165] (Method for measuring charge amount) As shown in Figure 1, 0.100 g of two-component developer for which triboelectric charge is to be measured is placed in a metal measurement container 2 with a 500 mesh (25 μm opening) screen 3 at the bottom, and the metal lid 4 is placed on top. The entire measurement container 2 at this stage is weighed and represented as Wl (g). Next, in the suction device 1 (at least the part in contact with the measurement container 2 is an insulator), suction is performed from the suction port 7, and the air flow control valve 6 is adjusted to set the pressure on the vacuum gauge 5 to 250 mmAq. Suction is continued in this state for a sufficient amount of time, preferably for 2 minutes, to remove the toner by suction. The potential of the electrometer 9 at this time is V (volts). Here, 8 is a capacitor with a capacity of C (μF). The entire measuring container after suction is weighed and expressed as W2 (g). The amount of triboelectric charge of this toner is calculated using the following formula. Frictional charge (mC / kg) = (C × V) / (W1 - W2)

[0166] <Evaluation of environmental dependency of toner charge amount> The ratio of the amount of charge between Condition 1 and Condition 2 (Condition 1 / Condition 2) and the ratio of the amount of charge between Condition 3 and Condition 2 (Condition 3 / Condition 2) were calculated, and each was evaluated according to the following evaluation criteria. (Evaluation criteria) A: Charge ratio is 0.80 or more B: Charge ratio is 0.65 or more and less than 0.80 C: Charge ratio is 0.50 or more and less than 0.65 D: Charge ratio is 0.40 or more and less than 0.50 E: Charge ratio is less than 0.40

[0167] [Table 7-1] [Table 7-2] The unit of charge is mC / kg. [Explanation of symbols]

[0168] 1 suction machine, 2 measuring container, 3 screen, 4 lid, 5 vacuum gauge, 6 air flow control valve, 7 suction port, 8 condenser, 9 electrometer

Claims

1. A toner comprising toner particles, the toner particles contain a binder resin, a resin A, a resin B, and a colorant having an azo group, the content of the resin A relative to 100.0 parts by mass of the binder resin in the toner particles is 0.1 parts by mass to 20.0 parts by mass; the content of the resin B relative to 100.0 parts by mass of the binder resin in the toner particles is 0.1 parts by mass to 20.0 parts by mass; The binder resin does not have a silyl group or a salicylic acid skeleton, The resin A has a structure represented by the following formula (1): the content of silicon atoms in the resin A is 0.02% by mass to 10.00% by mass, The resin B has a monovalent group having a salicylic acid structure. A toner characterized by: (In the formula (1), P 1 represents a polyester resin moiety; L 1 represents a single bond or a divalent linking group; R 1 to R 3 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxy group; m represents a positive integer; and when m is 2 or greater, a plurality of L 1 s, a plurality of R 1 s, a plurality of R 2 s, and a plurality of R 3 s may be the same or different.)

2. 2. The toner according to claim 1, wherein a mass ratio of the content of said resin A to the content of said resin B in said toner (resin A / resin B) is 0.05 or more and 50.00 or less.

3. The R １ ~R ３ 3. The toner according to claim 1, wherein at least one of the groups represents an alkoxy group or a hydroxy group having one or more carbon atoms.

4. 4. The toner according to claim 1, wherein the resin B is a polyester resin having a monovalent group having a salicylic acid structure or a styrene-acrylic resin having a monovalent group having a salicylic acid structure.

5. 5. The toner according to claim 1, wherein the weight average molecular weight of the resin A is 3,000 or more and 100,000 or less.

6. 6. The toner according to claim 1, wherein the weight average molecular weight of the resin B is 5,000 or more and 100,000 or less.

7. The colorant having an azo group is C.I. Pigment Yellow 74, C.I. Pigment Red 269, C.I. Pigment Yellow 155, C.I. Pigment Yellow 180, and C.I. Pigment Red 7. The toner according to claim 1, wherein the toner is at least one selected from the group consisting of 150.

Images