Toner

Abstract

Toner comprising a toner particle containing a binder resin, wherein the toner particle comprises a condensation product of an organosilicon compound, in time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particle, a normalized intensity of silicon ions (m / z 28) originating from the condensation product of the organosilicon compound, given by the following expression (I), of 7.00×10 -4 up to 3.00×10 -2 amounts; Normalized intensity λt of silicon ions (m / z 28) = {Ionic intensity λt (m / z 28) of silicon ions} / {Gesmation intensity λt from m / z 0.5 to 1850} a normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar-gas cluster ion beam Ar-GCIB under the following condition (A) 6.99×10 -4or less; (A) Acceleration voltage: 5 kV, Current: 6.5 nA, Grid size: 600×600 µm, Irradiation time: 5 seconds / cycle, Sputtering time: 250 seconds, the toner contains fine particles on the surface of the toner particles, and The fine particles of a polyvalent acid metal salt are a reaction product of a compound comprising at least one of the elements Ti and Al, and a polyvalent acid. wherein the condensation product of the organosilicon compound is a silane-modified resin R with the structure represented by the following formula (1); in formula (1) P 1 represents a styrene-acrylic resin segment or a polyester resin segment; L 1 represents a single bond or a divalent compound group; R 1 to R 3Each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 or more carbon atoms, an alkoxy group with 1 or more carbon atoms, an aryl group with 6 or more carbon atoms, or a hydroxy group; and m represents a positive integer; in a case where m is equal to or greater than 2, a plurality of L 1 , a plurality of R 1 , a plurality of R 2 and a plurality of R 3 each may be identical or different; however, Si is bonded to at least one carbon, and at least one of R 1 to R 3 is condensed with an organosilicon compound.

Description

Background of the invention; Field of the invention

[0001] The present disclosure relates to a toner used in recording methods that employ an electrophotographic method, an electrostatic recording method, or a toner beam system recording method. Description of the state of the art

[0002] Methods for visualizing image information via an electrostatic latent image, such as electrophotographic methods, have been used in copiers, multifunction devices and printers; in recent years, further requirements have been placed on such methods in order to achieve cost reductions and higher image quality.

[0003] In this context, the toner is required to reproduce the latent image faithfully. Precise control of the toner charge is crucial for this faithful reproduction. Insufficient control of the toner charge leads to defects such as fogging, where low-charge toner develops in areas without an image, and poor control, where overcharged toner fuses with the toner-bearing element. These are factors that prevent faithful reproduction of the latent image.

[0004] Triboelectric charging, in which the toner is charged by friction between the toner and a carrier or charging element (hereinafter collectively referred to as the charging element), has so far been extensively studied as a toner charging method.

[0005] However, since the friction between the charging element and the toner is not uniform, triboelectric charging can result in both overcharged and undercharged toner. This is because triboelectric charging only occurs in the areas where the toner and charging element are in contact.

[0006] Furthermore, triboelectric charging is highly susceptible to humidity, and the charge level can vary between low and high humidity environments. Since triboelectric charging is also very sensitive to the toner's fluidity, the charge level can change if the fluidity decreases, for example, due to toner deterioration from long-term use.

[0007] To solve these problems with the triboelectric charging method, investigations into the injection charging method were carried out. The injection charging method is a process in which the toner is charged by injecting charge due to the potential difference between the toner and the charging element.

[0008] In this case, if conductive pathways are present in the toner and from toner to toner, the toner as a whole can be charged evenly, instead of only charging the areas that are in contact with a charging element.

[0009] Since the amount of charge in injection charging can be freely controlled by changing the potential difference, the required charge level of a system can be easily achieved. Furthermore, because injection charging is resistant to the effects of humidity, environmental fluctuations in the charge level can be suppressed.

[0010] However, one problem with the injection charging method is the difficulty of achieving a coexistence of charge injection and charge conservation. This is due to the fact that the presence of conduction paths within and between toners facilitates the escape of the injected charge, so that the charge injection capability and the charge conservation capability are in a tension relationship.

[0011] JP 2005-148409 A discloses a toner in which the specific resistance is reduced at high voltage and discloses an injection charging method that uses this toner. One objective of the method described in this patent document is to eliminate the trade-off between charge injection capability and charge retention capability by performing only one charge injection method for the toner at a high voltage, at which the specific resistance of the toner is reduced.

[0012] From another point of view, JP 2019-133145 A discloses a toner in which the surface of a toner base particle is coated with metal particles and an organosilicon compound to achieve both control of loading properties and durability.

[0013] EP 3 929 659 A1 (post-publication prior art pursuant to Section 3 (2) PatG) relates to a toner comprising a toner particle comprising a resin A and an external additive A, wherein the resin A is a resin represented by a specific formula (1), the resin A is present on the surface of the toner particle, the external additive A is a fine particle containing silicon, the average value of the form factor SF-1 of the external additive A is between 105 and 120, and the average value of the form factor SF-2 of the external additive A is between 100 and 130. Summary of the invention

[0014] With regard to JP 2005-148409 A, precise control of the charge quantity was problematic because discharge is facilitated by the high voltage required in the charge injection process to achieve injection charge. Furthermore, there is limited freedom in designing the process voltage setting, as other processes must be carried out at lower voltages.

[0015] The toner disclosed in JP 2019-133145 A exhibits excellent performance when charged using a conventional triboelectric charging method, while at the same time the toner is unlikely to cause elemental contamination and exhibits excellent durability.

[0016] On the other hand, there are few means of injecting charge into a toner base particle, and consequently, the charge is easily retained on the toner particle surface. Therefore, the charge easily escapes through the metal particles on the toner particle surface, and charge retention becomes insufficient; accordingly, improvements are needed for the purpose of incorporation into an injection charging process.

[0017] According to the preceding, a toner that achieves a high degree of coexistence between charge injection capability and charge retention capability during injection charging has not yet been achieved, and further improvements are needed.

[0018] The present disclosure provides a toner that enables precise charge control and achieves high image quality by allowing a coexistence between charge injection capability and charge retention capability during the injection charging process.

[0019] The present disclosure relates to a toner comprising a toner particle containing a binder resin, wherein the toner particle comprises a condensation product of an organosilicon compound, in time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particle, a normalized intensity of silicon ions (m / z 28) originating from the condensation product of the organosilicon compound, given by the following expression (I), of 7.00×10 -4 up to 3.00×10 -2 amounts; normalized intensity of silicon ions (m / z 28) = {ion intensity (m / z 28) of silicon ions} / {gemation intensity from m / z 0.5 to 1850} a normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar-gas cluster ion beam Ar-GCIB under the following condition (A) 6.99×10 -4 or less; (A) Acceleration voltage: 5 kV, current: 6.5 nA, grid size: 600×600 µm, irradiation time: 5 seconds / cycle, sputtering time: 250 seconds, the toner contains fine particles on the toner particle surface, and the fine particles are fine particles of a polyvalent acid metal salt, which is a reaction product of a compound comprising at least one of the elements Ti and Al, and a polyvalent acid, wherein the condensation product of the organosilicon compound is a silane-modified resin R with the structure represented by the following formula (1); in formula (1) P represents 1 represents a styrene-acrylic resin segment or a polyester resin segment; L 1 represents a single bond or a divalent compound group; R 1 to R 3Each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 or more carbon atoms, an alkoxy group with 1 or more carbon atoms, an aryl group with 6 or more carbon atoms, or a hydroxy group; and m represents a positive integer; in a case where m is equal to or greater than 2, a plurality of L 1 , a plurality of R 1 , a plurality of R 2 and a plurality of R 3 each may be identical or different; however, Si is bonded to at least one carbon, and at least one of R 1 to R 3 is condensed with an organosilicon compound.

[0020] The present disclosure provides a toner that enables precise charge control and has the ability to achieve high image quality by allowing a coexistence between charge injection capability and charge retention capability during the injection charging process.

[0021] Further features of the present invention will become apparent from the following description of exemplary embodiments. Description of the embodiments

[0022] Unless otherwise specified, descriptions of numerical ranges such as "from XX to YY" or "XX to YY" within the scope of the present invention include the numbers at the upper and lower limits of the range.

[0023] When describing numerical value ranges in a stepwise manner, the upper and lower limits of the respective numerical value ranges can be combined arbitrarily.

[0024] For a toner to exhibit high injection charging capability, it is essential that charge transfer occurs only during the injection charging process and in no other process. The inventors hypothesized that for a toner to possess the aforementioned properties, it is necessary that charge can be injected not only near the toner surface but also within the toner during the injection charging process, and that it is unlikely that charge will escape from near the toner surface during processes other than injection charging.

[0025] As a result of careful research, the inventors discovered that a toner with the following configuration can achieve both injection and retention of the charge in the injection charging process.

[0026] In other words, the present disclosure relates to a toner comprising a toner particle containing a binder resin, wherein the toner particle comprises a condensation product of an organosilicon compound, in time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particle, a normalized intensity of silicon ions (m / z 28) originating from the condensation product of the organosilicon compound, given by the following expression (I), of 7.00×10 -4 up to 3.00×10 -2 amounts; normalized intensity of silicon ions (m / z 28) = {ion intensity (m / z 28) of silicon ions} / {gemation intensity from m / z 0.5 to 1850} a normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar-gas cluster ion beam Ar-GCIB under the following condition (A) 6.99×10 -4 or less; (A) Acceleration voltage: 5 kV, current: 6.5 nA, grid size: 600×600 µm, irradiation time: 5 seconds / cycle, sputtering time: 250 seconds, the toner contains fine particles on the toner particle surface, and the fine particles are fine particles of a polyvalent acid metal salt, which is a reaction product of a compound comprising at least one of the elements Ti and Al, and a polyvalent acid, wherein the condensation product of the organosilicon compound is a silane-modified resin R with the structure represented by the following formula (1); in formula (1) P represents 1 represents a styrene-acrylic resin segment or a polyester resin segment; L 1 represents a single bond or a divalent compound group; R 1 to R 3Each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 or more carbon atoms, an alkoxy group with 1 or more carbon atoms, an aryl group with 6 or more carbon atoms, or a hydroxy group; and m represents a positive integer; in a case where m is equal to or greater than 2, a plurality of L 1 , a plurality of R 1 , a plurality of R 2 and a plurality of R 3 each may be identical or different; however, Si is bonded to at least one carbon, and at least one of R 1 to R 3 is condensed with an organosilicon compound.

[0027] The inventors assume that the underlying mechanism looks like this.

[0028] In the toner configuration above, metal-containing fine particles with excellent conductivity present on the toner quickly acquire a large amount of charge when charge is injected into the injection charging process, after which the charge migrates to a condensation product of an organosilicon compound with a silyl group, which tends to become negatively charged, on the toner particle surface.

[0029] At this point, the metal-containing particles are excessively charged by the targeted application of a large amount of charge, as in injection charging. It is assumed that this also easily infuses charge into the condensation product of an organosilicon compound, which is located near the metal-containing particles but not in contact with them, so that even a small amount of the condensation product of an organosilicon compound can be expected to produce a charging effect.

[0030] Furthermore, the condensation product of an organosilicon compound interacts with a binder resin, thereby promoting the transfer of charge into the toner. This series of currents allows charge to be injected uniformly and rapidly from the metal-containing particles into the toner via a small amount of the organosilicon compound condensation product located near the toner particle surface, thus achieving a high charge injection capability.

[0031] Meanwhile, it is assumed that the highly conductive, metal-containing fine particles represent starting points for charge leakage after the injection charging process. By limiting the condensation product of an organosilicon compound, which readily mediates charge transfer, to a very small amount near the toner particle surface, it becomes possible to minimize the transfer of charge from the interior of the toner to the toner surface and the transfer of charge originating from the contact between the condensation product of an organosilicon compound and the metal-containing fine particles.

[0032] This means that charge leakage from inside the toner can be suppressed, thus achieving a high charge retention capacity.

[0033] A toner cartridge is explained in terms of the mechanism described above.

[0034] The condensation product of an organosilicon compound is a silane-modified resin R with the structure represented by the following formula (1). The efficiency of charge propagation into the toner particle is improved and the charge quantity is further increased when the toner particle contains the silane-modified resin R as the condensation product of an organosilicon compound.

[0035] In the formula (1) above, P represents 1 represents a polymer segment; L 1 represents a single bond or a divalent compound group; R 1 to R 3 Each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 or more carbon atoms, an alkoxy group with 1 or more carbon atoms, an aryl group with 6 or more carbon atoms, or a hydroxy group; m represents a positive integer; in a case where m is equal to or greater than 2, a plurality of L 1, a plurality of R 1 , a plurality of R 2 and a plurality of R 3 They may each be identical or different. However, Si is bonded to at least one carbon and at least one of R 1 to R 3 is condensed with an organosilicon compound.

[0036] If at least one of R 1 to R 3 When condensed with an organosilicon compound, the group condensed with the organosilicon compound has an -O-Si≡ structure.

[0037] From R 1 to R 3 In the above formula (1), at least one group preferably represents an alkoxy group with one or more carbon atoms or a hydroxyl group. It is more preferred that the groups R 1 to R 3 , which are not condensed with an organosilicon compound, each independently represent an alkoxy group with 1 or more carbon atoms or a hydroxy group.

[0038] Among the substituents mentioned above, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 4. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 4, more preferably 1 to 3, and is particularly preferably 1 or 2. The number of carbon atoms in the aryl group is preferably 6 to 14, more preferably 6 to 10.

[0039] The silicon content in resin R is preferably 0.02 wt% to 10.00 wt%. The content is preferably 0.10 wt% to 5.00 wt% and even more preferably 0.50 wt% to 2.00 wt%.

[0040] The resin content R, based on 100.0 parts by mass of the binder resin, is preferably 0.10 parts by mass to 10.00 parts by mass, more preferably 0.20 parts by mass to 5.0 parts by mass and even more preferably 0.50 parts by mass to 2.0 parts by mass.

[0041] This is P 1in formula (1) a styrene-acrylic resin segment or a polyester resin segment. P 1 This could, for example, be a hybrid resin segment made of a polyester resin and a styrene-acrylic resin. It is more preferred that P 1 contains a polyester resin segment. In a case where P 1 Since it is a polyester resin segment, the interactions with the binder resin are high, the injection charging performance is further improved, and a high charge quantity can be obtained even at a low voltage.

[0042] If MwA denotes the weight-average molecular weight of the silane-modified resin R with the structure of formula (1), MwA is preferably between 8000 and 50000. In a case where MwA is 8000 or higher, the amount of the low molecular weight component is lower and the heat-resistant shelf life is slightly improved. If MwA is 50000 or less, the molecules exhibit high mobility and are easily arranged spatially after fixation; the adhesiveness of the output paper is thereby slightly improved.

[0043] Preferably, MwA is between 12,000 and 30,000. MwA can be controlled by changing the reaction temperature, reaction time, monomer composition, and the amount of initiator in the resin, or the like.

[0044] Any method can be used to form the silane-modified resin R with the structure of formula (1); examples of this are the following methods.

[0045] The silane-modified resin R can be formed according to a process in which a carboxyl group in the resin is reacted with an aminosilane coupling agent, according to a process in which an ethylene-unsaturated bonding segment in the resin or a monomer with an ethylene-unsaturated bond and a (meth)acrylsilane coupling agent are polymerized, according to a process in which a hydroxyl group in the resin and an isocyanate-based silane coupling agent are reacted, and according to a process in which an isocyanate group in the resin is reacted with an aminosilane coupling agent.

[0046] Examples of aminosilane coupling agents include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane and 3-aminopropylmethoxydimethylsilane.

[0047] Examples of (meth)acrylsilane coupling agents include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-acryloxyoctyltriethoxysilane, 8-methacryloxyoctyltriethoxysilane, 3-[(Triethoxysilyl)methyl acrylate, 3-(triethoxysilyl)methyl methacrylate, 3-[dimethoxy(methyl)silyl]propyl acrylate, 3-[dimethoxy(methyl)silyl]propyl methacrylate, [dimethoxy(methyl)silyl]methyl acrylate, [dimethoxy(methyl)silyl]methyl methacrylate and 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane.

[0048] Examples of isocyanate-based coupling agents include isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyldimethoxysilane.

[0049] In a case where the P 1 -Structure in the silane-modified resin R with the structure of formula (1) is a polyester resin segment, include examples of the condensation polymerization monomer that can be used to produce the polyester resin segment, polyhydric carboxylic acids and polyhydric alcohols.

[0050] Examples of polyhydric carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenedioacetic acid, m-phenyldiglycolic acid, p-phenyldiglycolic acid, o-phenyldiglycolic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, and naphthalene-1,5-dicarboxylic acid. Naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid and cyclohexanedicarboxylic acid.

[0051] Examples of polyhydric carboxylic acids other than dicarboxylic acids include trimellitic acid, pyromellitic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid and pyrene tetracarboxylic acid.

[0052] Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, isosorbide, trimethylolethane, and trimethylolpropane. 1,3,5-Trihydroxymethylbenzene, Bisphenol A, Bisphenol A ethylene oxide adducts, Bisphenol A propylene oxide adducts, hydrogenated Bisphenol A, hydrogenated Bisphenol A ethylene oxide adducts and hydrogenated Bisphenol A propylene oxide adducts.

[0053] The polyester resin is not particularly limited, but is preferably a condensate of a dialcohol and a dicarboxylic acid. The polyester resin is preferably, for example, a polyester resin with the structure represented by the following formula (6), and at least one of the structures selected from the group consisting of the structures represented by the following formulas (7) to (9) (several structures may be selected). Alternatively, the polyester resin may be a polyester resin with a structure represented by the following formula (10).

[0054] In formula (6) R represents 9 an alkylene group, an alkanylene group, or an arylene group. In formula (7), R represents 10 represents an alkylene group or a phenylene group. In formula (8), R represents 18an ethylene group or a propylene group. Furthermore, x and y are integers equal to or greater than 0, such that the average value of x+y lies between 2 and 10. In formula (10), R represents 11 represents an alkylene group or an alkenylene group.

[0055] Examples of the alkylene group (preferably with 1 to 12 carbon atoms) for R 9 in formula (6) include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group and 1,3-cyclopentylene, 1,3-cyclohexylene and 1,4-cyclohexylene groups.

[0056] Examples of the alkenylene group (preferably with 2 to 4 carbon atoms) for R 9Formula (6) includes a vinylene group, a propenylene group and a 2-butenylene group.

[0057] Examples of the arylene group (preferably with 6 to 12 carbon atoms) for R 9 in formula (6) 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.

[0058] R 9 In formula (6), the compound can be substituted with a substituent. In this case, examples of the substituent include a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and a combination thereof.

[0059] Examples of the alkylene group (preferably with 1 to 12 carbon atoms) for R 10Formula (7) includes a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group and 1,3-cyclopentylene, 1,3-cyclohexylene and 1,4-cyclohexylene groups.

[0060] Examples of the phenylene group for R 10 in formula (7) include a 1,4-phenylene group, a 1,3-phenylene group and a 1,2-phenylene group.

[0061] R 10 In formula (7), the compound can be substituted with a substituent. In this case, examples of the substituent include a methyl group, an alkoxy group, a hydroxy group, a halogen atom, and a combination thereof.

[0062] Examples of the alkylene group (preferably with 1 to 12 carbon atoms) for R 11in formula (10) include a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a hexamethylene group, a neopentylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group and a 1,4-cyclohexylene group.

[0063] Examples of the alkenylene group (preferably with 2 to 40 carbon atoms) for R 11Formula (10) includes a vinylene group, a propenylene group, a butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a hexadienylene group, a heptenylene group, an octanylene group, a decenylene group, an octadecenylene group, an eicosenylene group, and a triacontenylene group. These alkenylene groups can have a linear, branched, or cyclic structure. The double bond can be located at any position as long as at least one double bond is present.

[0064] R 11 In formula (10), the atom can be substituted with a substituent. In this case, examples of the substituent that can be used for substitution include an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, and a combination thereof.

[0065] If the P 1Since the structure is a styrene-acrylic resin, the monomers are not particularly limited, and well-known monomers can be used. For example, the following monomers can be used.

[0066] Styrene derivatives, such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene;

[0067] Acrylic-polymerizable monomers, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl 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, dibutyl phosphate ethyl acrylate, 2-hydroxyethyl acrylate, and 2-benzoyloxyethyl acrylate; and

[0068] Methacrylate-polymerizable monomers, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl phosphate ethyl methacrylate, 2-hydroxy ethyl methacrylate and dibutyl phosphate ethyl methacrylate.

[0069] The divalent compound group formed by L 1 The possibilities that can be represented in formula (1) are not particularly limited, and examples include the structures represented by the following formulas (2) to (5). In these cases, the injection charge performance can be further improved, and a high charge quantity can even be achieved at low voltage. This can probably be attributed to a high interaction with the binder resin, whereby the charge is distributed more uniformly to the P 1 -segment is delivered.

[0070] The atom of the compound group that is bonded to Si in formula (1) is preferably a carbon atom.

[0071] R 5 In formula (2), represents a single bond, an alkylene group, or an arylene group. (*) represents a bond segment to P. 1 in formula (1), and (**) represents a bonding segment to a silicon atom in formula (1).

[0072] R 6 In formula (3), a single bond, an alkylene group, or an arylene group is represented. (*) represents a bond segment to P. 1 in formula (1), and (**) represents a bonding segment to a silicon atom in formula (1).

[0073] R 7 and R 8 In formulas (4) and (5), each independently represents an alkylene group, an arylene group, or an oxyalkylene group. (*) represents a bond segment to P 1in formula (1), and (**) represents a bonding segment to a silicon atom in formula (1).

[0074] Among the aforementioned is L 1 preferably a divalent compound group represented by the above formula (2) which contains an amide bond.

[0075] The structure represented by formula (2) is a divalent compound group containing an amide bond.

[0076] The compound group can be formed, for example, by the reaction of a carboxyl group in the resin with an aminosilane.

[0077] The aminosilane is not particularly limited, and examples include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-6-(aminohexyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, 3-aminopropylsilicon and the like.

[0078] The alkylene group (preferably with 1 to 12 carbon atoms, more preferably with 2 to 4 carbon atoms) in R 5 is not particularly limited and can, for example, be an alkylene group containing an -NH group.

[0079] The arylene group (preferably with 6 to 12 carbon atoms, more preferably with 6 to 10 carbon atoms) in R 5 is not particularly limited and can, for example, be an arylene group containing a heteroatom.

[0080] The structure represented by formula (3) is a divalent compound group containing a urethane bond.

[0081] The compound group can be formed, for example, by the reaction of a hydroxy group in the resin with an isocyanate silane.

[0082] The isocyanate silane is not particularly limited, and examples include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyldimethylethoxysilane and the like.

[0083] The alkylene group (preferably with 1 to 12 carbon atoms, more preferably with 2 to 4 carbon atoms) in R 6 is not particularly limited and can, for example, be an alkylene group containing an -NH group.

[0084] The arylene group (preferably with 6 to 12 carbon atoms, more preferably with 6 to 10 carbon atoms) in R 6 is not particularly limited and can, for example, be an arylene group containing a heteroatom.

[0085] The structure represented by formula (4) or (5) is a divalent compound group containing a bond grafted onto an ester bond in the resin.

[0086] The compound group is formed, for example, by an epoxysilane insertion reaction.

[0087] The term "epoxysilane insertion reaction" refers to a reaction that includes the insertion of an epoxy group of epoxysilane into an ester bond contained in a main chain of a resin. Furthermore, the term "insertion reaction" as used here is described in the "Journal of Synthetic Organic Chemistry, Japan," Vol. 49, No. 3, p. 218, 1991, as "an insertion reaction of an epoxy compound into an ester bond in a polymer chain."

[0088] The reaction mechanism of the epoxysilane insertion reaction can be represented by the following model diagram.

[0089] In the diagram above, D and E denote the components of the resin and F the component of the epoxy compound.

[0090] Two types of compounds are formed through α-cleavage and β-cleavage during the ring opening of the epoxy group in the diagram. In both cases, a compound is obtained in which an epoxy group is inserted into an ester bond in a resin; in other words, a compound in which a component of the epoxy compound other than the epoxy segment is grafted onto the resin.

[0091] The epoxysilane is not particularly limited and can be, for example, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like.

[0092] The alkylene group (preferably with 1 to 12 carbon atoms, more preferably with 2 to 4 carbon atoms) in R 7 and R 8 is not particularly limited and can, for example, be an alkylene group containing an -NH group.

[0093] The arylene group (preferably with 6 to 12 carbon atoms, more preferably with 6 to 10 carbon atoms) in R 7 and R 8 is not particularly limited and can, for example, be an arylene group containing a heteroatom.

[0094] The oxyalkylene group (preferably with 1 to 12 carbon atoms, more preferably with 2 to 4 carbon atoms) in R 7 and R 8 is not particularly limited and can, for example, be an oxyalkylene group containing an -NH group.

[0095] A normalized intensity of silicon ions (m / z 28), given by expression (I) and derived from a condensation product of an organosilicon compound, must be in the range of 7.00×10⁻⁸ during time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particle. -4 up to 3.00×10 -2 lay.

[0096] Silicon ion normalized intensity (m / z 28)={ion intensity (m / z 28) of silicon ions} / {total ion intensity of m / z from 0.5 to 1850}...(I)

[0097] If the normalized intensity of silicon ions (m / z 28) is lower than 7.00×10 -4 If the normalized intensity of silicon ions (m / z 28) is higher than 3.00×10 -2 If this is the case, the charge retention capability cannot be achieved, and as a result, it is difficult to achieve both the charge injection capability and the charge retention capability.

[0098] To achieve a higher charge retention capacity, the normalized intensity of the silicon ions (m / z 28) is preferably 7.00×10 -4 up to 8.00×10 -3 and more strongly preferred by 8.00×10 -4 and 8.00×10 -3 .

[0099] A normalized intensity within these ranges indicates that the amount of silicon ions on the toner particle surface is much lower than in conventional techniques. It is assumed that a normalized intensity within the aforementioned ranges can be achieved, and as a result, both charge injection and charge retention capabilities can be maintained by employing measures such as using a very small amount of organosilicon compound compared to conventional methods, controlling the hydrolysis of the organosilicon compound, shortening the condensation time, and similar techniques.

[0100] Furthermore, the normalized intensity of the silicon ions (m / z 28) in time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar-gas cluster ion beam Ar-GCIB must be 6.99×10 -4 or less.

[0101] (A) Acceleration voltage: 5 kV, Current: 6.5 nA, Grid size: 600×600 µm, Irradiation time: 5 sec / cycle, Sputtering time: 250 sec

[0102] Silicon ions originating from a condensation product of an organosilicon compound present inside the toner particle can be evaluated by sputtering under condition (A); the less condensation product of an organosilicon compound present inside the toner particle, the better the charge retention capacity. Preferably, the normalized intensity is 6.00 × 10 -4 or less. The lower limit of the normalized intensity is not particularly restricted, but is preferably around 1.00 × 10⁻⁶. -4 or higher, and more strongly preferred at 2.00×10 -4 or higher.

[0103] Any method can be used to obtain a toner particle with the desired normalized silicon ion intensity (m / z 28). In a case where a silane-modified resin R is used as the condensation product of an organosilicon compound, examples of such a method include adding the resin R in a step of dissolving or dispersing a polymerizable monomer capable of generating a binder resin.

[0104] In a case where a condensation product of a silane coupling agent is used as the condensation product of an organosilicon compound, examples include a process in which the condensation polymerization is carried out after the addition of a silane coupling agent, as appropriately in a step of dissolving or dispersing a polymerizable monomer, or in a step of obtaining a toner particle by polymerizing a polymerizable monomer. Other processes include a process involving the addition of a silane coupling agent to a toner particle dispersion with condensation polymerization.

[0105] There may be an optimal pH value for the condensation polymerization reaction of the organosilicon compound, and accordingly, the reaction can be effectively carried out by performing the condensation polymerization of the organosilicon compound at an optimal pH value for the condensation polymerization reaction.

[0106] The method for adding the organosilicon compound, such as a silane coupling agent, may include adding the organosilicon compound in its as-is state or prior mixing of the organosilicon compound with an aqueous medium and subsequent addition of the resulting hydrolyzed product.

[0107] The method for controlling the normalized intensity of silicon ions (m / z 28) near the toner particle surface or inside the toner particle may, for example, include controlling the amount added of the organosilicon compound, the polymerization conversion ratio of the polymerizable monomer, the hydrolysis time, or the condensation polymerization time after addition of the organosilicon compound to form the condensation product of an organosilicon compound.

[0108] Furthermore, the toner exhibits fine particles on its surface. These fine particles are particles of a polyvalent metal acid salt, which is a reaction product of a compound containing at least one of the elements Ti and Al, and a polyvalent acid.

[0109] These are fine particles of a polyvalent acid metal salt, which are a reaction product of a polyvalent acid and a compound containing Ti and / or Al, preferably with Ti as the metal element, in order to achieve a higher overall injection charging rate in the toner and an even more uniform charging rate. Even more preferably, the polyvalent acid in the aforementioned fine particles of a polyvalent acid metal salt is phosphoric acid, since in this case an even more uniform charge distribution is achieved.

[0110] The fine particle content is preferably from 0.01 parts by mass to 5.00 parts by mass, more preferably from 0.02 parts by mass to 3.00 parts by mass and even more preferably from 0.10 parts by mass to 0.30 parts by mass, based on 100 parts by mass of the toner particle.

[0111] The polyhydric acids known so far can be used as polyhydric acids without any particular restrictions.

[0112] The polyhydric acid preferably contains an inorganic acid. Inorganic acids have a more rigid molecular structure than organic acids and therefore hardly change their properties during long-term storage. The injectable charge capability can thus be maintained stably even after prolonged storage.

[0113] Polyhydric acids include inorganic acids, e.g. phosphoric acid (tribasic), carbonic acid (dibasic) and sulfuric acid (dibasic), as well as organic acids such as dicarboxylic acids (dibasic) and tricarboxylic acids (tribasic).

[0114] Organic acids include, for example, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, cortic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid and terephthalic acid, and tricarboxylic acids such as citric acid, aconitic acid and trimellitic anhydride.

[0115] Among the aforementioned, at least one selection from the group consisting of the inorganic acids phosphoric acid, carbonic acid and sulfuric acid is preferred, with phosphoric acid being particularly preferred.

[0116] Specific examples of polyvalent acid metal salts include metal phosphate salts, such as titanium phosphate compounds and aluminum phosphate compounds; metal sulfate salts, such as titanium sulfate compounds and aluminum sulfate compounds; metal carbonate salts, such as titanium carbonate compounds and aluminum carbonate compounds; and oxalate metal salts, such as titanium oxalate compounds. Titanium phosphate compounds are particularly preferred among the aforementioned.

[0117] The method for obtaining the fine particles of a polyvalent acid metal salt is not particularly limited, and a known method can be used. A preferred method involves reacting polyvalent acid ions and a metal compound, representing a metal source, in an aqueous medium to obtain fine particles of a polyvalent acid metal salt.

[0118] If the fine particles of a polyvalent acid metal salt are obtained according to the above procedure, a conventionally known metal compound can be used as a metal source without special restrictions, as long as the metal compound can yield a polyvalent acid metal salt by reaction with polyvalent acid ions.

[0119] Specific examples include metal chelates, such as titanium lactate, titanium tetraacetylacetonate, ammonium titanium lactate, titanium triethanolamine, zirconium lactate, ammonium zirconium lactate, aluminum lactate, aluminum trisacetylacetonate and copper lactate, and metal alkoxides, such as titanium tetraisopropoxide, titanium ethoxide, zirconium tetraisopropoxide and aluminum trisopropoxide.

[0120] Metal chelates are preferred among those mentioned above because their reaction is easy to control and they react quantitatively with the polyvalent acid ion. Lactic acid chelates, e.g., titanium lactate, zirconium lactate, etc., are preferred from the point of view of solubility in aqueous media.

[0121] An ion of the aforementioned polyvalent acids can be used as the polyvalent acid ion. Regarding its form when added to an aqueous medium, the polyvalent acid can be added as such, or a water-soluble polyvalent acid metal salt can be added to the aqueous medium and dissociate within it.

[0122] If the fine particles of a polyvalent acid metal salt are obtained by the procedure described above, the number-averaged particle diameter DA of the fine particles of a polyvalent acid metal salt can be controlled, for example, by the reaction temperature and the concentration of the starting material during the synthesis of the fine particles of a polyvalent acid metal salt.

[0123] The number-averaged particle diameter DA of the fine particles of a polyvalent acid metal salt is preferably from 3 nm to 100 nm, more preferably from 5 nm to 30 nm and even more preferably from 8 nm to 20 nm.

[0124] The total content of calcium and magnesium elements in the toner particle, measured by an inductively coupled plasma atomic emission spectrometer, is preferably 23 µmol / g or less, and more preferably 20 µmol / g or less. The lower limit is not particularly restricted, but is preferably 0 µmol / g or more, and more preferably 2 µmol / g or more.

[0125] The total content within the above-mentioned ranges indicates that the amount of metal elements representing charge leakage sources is low near the toner particle surface, thus improving charge retention and making both charge retention and injection charging performance even easier to achieve.

[0126] A calcium and / or magnesium compound can be used as a dispersant when the toner particle is produced in an aqueous medium. The aforementioned content can be controlled, for example, based on the amount of these dispersants used and by removing the dispersant through washing the toner particle, etc. Method for producing a toner particle

[0127] A process for producing a toner particle is described. A known method, such as a kneading-powdering process or a wet production process, can be used for producing the toner particle. A wet production process is preferable from the perspective of standardizing the particle diameter and controlling the shape. Examples of wet production processes include a suspension polymerization process, a solution-suspension process, an emulsion polymerization-aggregation process, an emulsion aggregation process, and the like; a suspension polymerization process is preferred among the aforementioned.

[0128] The following describes a process for producing a toner particle using a suspension polymerization process.

[0129] First, a polymerizable monomer capable of obtaining a binder resin and various materials are mixed as required, and a dispersing device is used to produce a polymerizable monomer composition in which the above-mentioned materials are dissolved or dispersed.

[0130] Examples of the above-mentioned materials include dyes, wax release agents, charge control agents, polymerization initiators, chain transfer agents, and the like.

[0131] Examples of dispersing devices include homogenizers, ball mills, colloid mills, and ultrasonic dispersing devices.

[0132] Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles to produce droplets of the polymerizable monomer composition using a high-speed disperser, such as a high-speed stirrer or ultrasonic disperser (granulation step).

[0133] The polymerizable monomer is then polymerized in the droplet of the polymerizable monomer composition to obtain a toner particle (polymerization state).

[0134] The polymerization initiator can be mixed into the polymerizable monomer composition during the preparation of the polymerizable monomer composition or immediately before droplet formation in the aqueous medium.

[0135] Furthermore, it can also be added during granulation into droplets or after completion of granulation, i.e. immediately before the start of the polymerization reaction, optionally dissolved in the polymerizable monomer or another solvent.

[0136] Once the resin particles have been obtained by polymerization of the polymerizable monomer, a solvent removal process can be carried out as needed to obtain a dispersion of the toner particles.

[0137] The weight-averaged particle diameter (D4) of the toner particle is preferably from 4.0 µm to 12.0 µm, more preferably from 5.0 µm to 8.0 µm.

[0138] The average circularity of the toner particle is preferably from 0.940 to 0.995, more preferably from 0.950 to 0.990 and even more preferably from 0.970 to 0.990.

[0139] The glass transition temperature Tg of the toner particle is preferably from 40°C to 70°C, more preferably from 50°C to 60°C.

[0140] The components of the toner particle are explained below. Binder resin

[0141] Preferred examples of binder resins include vinyl resins and polyester resins. Examples of vinyl resins, polyester resins, and other binder resins are the resins and polymers listed below.

[0142] Monopolymers of styrene and its substitutes, such as polystyrene and polyvinyltoluene; Styrene copolymers, such as styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers, styrene-octyl acrylate copolymers, Styrene-dimethylaminoethyl acrylate copolymers, styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymers, styrene-dimethylaminoethyl methacrylate copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, Styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers and Styrene-maleic acid ester copolymers;as well as polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resins, polyamide resins, epoxy resins, polyacrylic resins, rosin, modified rosin, terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins. These binder resins can be used individually or in combination.

[0143] Examples of polymerizable monomers that can be used to produce a vinyl resin include styrene monomers, such as styrene and α-methylstyrene; acrylate esters, such as methyl acrylate and butyl acrylate; methacrylate esters, such as methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate; unsaturated carboxylic acids, such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids, such as maleic acid; unsaturated dicarboxylic anhydrides, such as maleic anhydride; nitrile-based vinyl monomers, such as acrylonitrile; halogenated vinyl monomers, such as vinyl chloride; and nitro-based vinyl monomers, such as nitrostyrene.

[0144] In addition to these monomers, the ones listed above for P can also be used. 1 The described monomers are used.

[0145] The binder resin preferably contains a carboxyl group and is preferably a resin produced using a polymerizable monomer containing a carboxyl group.

[0146] Examples of polymerizable monomers containing a carboxyl group include, for example, vinyl carboxylic acids such as acrylic acid, methacrylic acid, α-ethylacrylic acid, and crotonic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid; and unsaturated dicarboxylic acid monoester derivatives such as monoacryloyloxyethyl succinate, monomethacryloyloxyethyl succinate, monoacryloyloxyethyl phthalate, and monomethacryloyloxyethyl phthalate.

[0147] A polyester resin produced by condensation polymerization of a carboxylic acid component and an alcohol component, as listed below, can be used as a polyester resin. 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, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, glycerol, trimethylolpropane, and pentaerythritol.

[0148] The polyester resin can be a polyester resin containing a urea group. Preferably, the polyester resin has an uncapped carboxyl group, for example at one end.

[0149] In addition to these monomers, the ones listed above for P can also be used. 1 The described monomers are used.

[0150] To control the molecular weight of the binder resin, a crosslinking agent can be added during the polymerization of the polymerizable monomer.

[0151] For example, 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 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate (MANDA, manufactured by Nippon Kayaku Co., Ltd.) and the above-mentioned acrylates, which are converted into methacrylates.

[0152] Preferably, the amount of crosslinking agent added ranges from 0.001 parts by mass to 15.000 parts by mass, based on 100 parts by mass of the polymerizable monomer. Release agent

[0153] The toner particle preferably contains a release agent. The toner particle preferably contains an ester wax with a melting point of 60°C to 90°C. Such a wax exhibits excellent compatibility with the binder resin and therefore readily provides a plasticizing effect.

[0154] Examples of ester waxes include waxes with a fatty acid ester as the main component, such as carnauba wax and Montana ester wax; wholly or partially deacidified products of the acid component of fatty acid esters, such as deacidified carnauba wax; methyl ester compounds with a hydroxyl group obtained by hydrogenation of a vegetable oil, and the like; saturated fatty acid monoesters, such as stearyl stearate and behenyl behenate; diesterification products of saturated aliphatic dicarboxylic acids and saturated aliphatic alcohols, such as dibehenyl sebacate, distearyldodecanedioate, and distearyloctadecanedioate; and diesterification products of saturated aliphatic diols and saturated aliphatic monocarboxylic acids, such as nonanediol dibehenate and dodecanediol distearate.

[0155] Preferably among the aforementioned, the wax contains a bifunctional ester wax (diester) with two ester bonds in the molecular structure.

[0156] The bifunctional ester wax is an ester compound consisting of a dihydric alcohol and an aliphatic monocarboxylic acid or an ester compound consisting of a dihydric carboxylic acid and an aliphatic monoalcohol.

[0157] Specific examples of aliphatic monocarboxylic acids include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, oleic acid, vaccenic acid, linoleic acid and linolenic acid.

[0158] Specific examples of aliphatic monoalcohols include myristyl alcohol, cetanol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol and triacontanol.

[0159] Specific examples of divalent carboxylic acids include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (sebacic acid), dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosandioic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0160] Specific examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, bisphenol A, and hydrogenated bisphenol A.

[0161] Other examples of release agents that can be used include petroleum waxes and their derivatives, such as paraffin wax; microcrystalline wax and petrolatum; montan wax and its derivatives; hydrocarbon waxes and their derivatives obtained by the Fischer-Tropsch process; polyolefin waxes and their derivatives, such as polyethylene and polypropylene; natural waxes and their derivatives, such as carnauba wax and candelilla wax; and fatty acids, such as higher aliphatic alcohols, stearic acid, and palmitic acid.

[0162] The content of the release agent is preferably from 5.0 parts by mass to 20.0 parts by mass based on 100.0 parts by mass of the binder resin. Dye

[0163] The toner particle may contain a colorant. The colorant is not particularly limited, and well-known colorants such as those listed below can be used.

[0164] Examples of yellow pigments include yellow iron oxide and condensed azo compounds, such as Navels Yellow, Naphthol Yellow S, Hanza Yellow G, Hanza Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, and Tartrazine Lake, as well as isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. The following are listed in detail.

[0165] CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168 and 180.

[0166] Examples of red pigments include Indian red, condensed azo compounds such as Permanent Red 4R, Lithol Red, Pyrazolone Red, Watching Red calcium salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, and the like, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. The following are listed in detail.

[0167] CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254.

[0168] Examples of blue pigments include copper phthalocyanine compounds and their derivatives, such as Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, metal-free Phthalocyanine Blue, partial Phthalocyanine Blue chloride, Fast Sky Blue, Indathrene Blue BG, and the like, as well as anthraquinone compounds, basic dye lake compounds, and the like. The following are listed in detail.

[0169] CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66. Examples of black pigments include carbon black and aniline black. These dyes can be used individually or in mixtures, and also in solid solution.

[0170] The content of the colorant is preferably 3.0 parts by mass to 15.0 parts by mass based on 100.0 parts by mass of the binder resin. External additive

[0171] Various organic or inorganic fine powders can be used simultaneously as external additives in the toner particle, provided that the above-mentioned properties or effects are not impaired.

[0172] The following describes methods for measuring various physical properties.

[0173] Method for measuring the weight-averaged particle diameter (D4) and the number-averaged particle diameter (D1) of a toner particle

[0174] The weight-averaged particle diameter (D4) and the number-averaged particle diameter (D1) of the toner particle are determined as follows.

[0175] The measuring instrument used is a “Coulter Counter Multisizer 3” (registered trademark, Beckman Coulter, Inc.), a precision instrument for measuring particle size distribution, which operates according to the method of electrical pore resistance and is equipped with a 100-µm aperture tube.

[0176] The measurement conditions are set and the measurement data is evaluated using the associated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter, Inc.). Measurements are performed in 25,000 channels, representing the number of effective measurement channels.

[0177] The aqueous electrolyte solution used for the measurements is prepared by dissolving sodium chloride of a special quality in deionized water to a concentration of 1.0%, e.g. “ISOTON II” (Beckman Coulter, Inc.) can be used.

[0178] The associated software is configured as follows before measurement and analysis.

[0179] On the screen “modify the standard operating method (SOMME)” in the associated software, the total number of particles in control mode is set to 50,000 particles; the number of measurements is set to 1; and the Kd value is set to the value obtained with “standard particle 10.0 µm” (Beckman Coulter, Inc.).

[0180] The threshold and noise level are automatically set by pressing the "threshold value / noise level measurement" button. Additionally, the current is set to 1600 µA; the gain is set to 2; the electrolyte solution is set to ISOTON II; and the "post-measurement aperture tube flush" checkbox is selected.

[0181] On the screen “setting conversion from pulses to particle diameter” of the associated software, the bin interval is set to the logarithmic particle diameter; the particle diameter bin is set to 256 particle diameter bins; and the particle diameter range is set to 2 µm to 60 µm.

[0182] The specific measurement procedure is as follows. (1) 200.0 mL of the aqueous electrolyte solution are placed in a 250 mL round-bottomed glass vessel intended for the Multisizer 3, which is placed in the sample rack and stirred counterclockwise at 24 revolutions per second using the stirring rod. Impurities and air bubbles in the aperture tube are removed beforehand using the "aperture tube flush" function of the associated software. (2) 30.0 mL of the aqueous electrolyte solution are placed in a 100 mL flat-bottomed beaker. To this, 0.3 mL of a dilution prepared by triple (mass) dilution with deionized water of “Contaminon N” (a 10% aqueous solution of a neutral pH 7 cleaning agent for cleaning precision instruments, containing a non-ionic surfactant, an anionic surfactant and an organic builder, from Wako Pure Chemical Industries, Ltd) is added as a dispersant. (3) An “Ultrasonic Dispersion System Tetra 150” (Nikkaki Bios Co., Ltd.) is prepared; this is an ultrasonic disperser with an electrical power of 120 W and is equipped with two oscillators (oscillation frequency = 50 kHz) arranged so that the phases are shifted by 180°. 3.3 L of deionized water and 2.0 mL of Contaminon N are added to the water tank of the ultrasonic disperser. (4) The beaker described in (2) is inserted into the beaker holder opening of the ultrasonic disperser and the ultrasonic disperser is started. The vertical position of the beaker is adjusted so that the resonance state of the surface of the aqueous electrolyte solution in the beaker is at its maximum. (5) While the aqueous electrolyte solution in the beaker prepared according to (4) is irradiated with ultrasound, 10 mg of toner particles are added to the aqueous electrolyte solution in small aliquots and dispersed. The ultrasonic dispersion is continued for a further 60 seconds. The water temperature in the water tank is regulated between 10°C and 40°C as required during the ultrasonic dispersion. (6) Using a pipette, the aqueous electrolyte solution prepared in (5), containing the dispersed toner particles, is dropped into the round-bottomed beaker, which has been inserted into the sample rack as described in (1), setting a measurement concentration of 5%. The measurement is then carried out until the number of measured particles reaches 50,000. (7) The measurement data are analyzed by the special software supplied with the instrument, and the weight-averaged particle diameter (D4) and the number-averaged particle diameter (D1) are calculated. If the software is set to Graph / Volume%, the "average diameter" displayed on the "analysis / volumetric statistical value (arithmetic average)" screen is the weight-averaged particle diameter (D4). If the software is set to Graph / Number%, the "average diameter" displayed on the "analysis / numerical statistical value (arithmetic average)" screen is the number-averaged particle diameter (D1). Methods for measuring the glass transition temperature (Tg)

[0183] The glass transition temperature (Tg) of, for example, the binder resin and the toner is measured using a differential scanning calorimeter (hereinafter also referred to as "DSC").

[0184] The glass transition temperature is measured using DSC according to JIS K 7121 (international standard: ASTM D 3418-82).

[0185] For this measurement, a “Q1000” (TA Instruments) is used, whereby the melting points of indium and zinc are used to correct the temperature of the detection part of the instrument and the heat of fusion of indium is used to correct the amount of heat.

[0186] For the measurement, a sample of 10 mg is weighed precisely and placed in an aluminum dish; an empty aluminum dish serves as a reference.

[0187] In an initial warm-up process, the measurement is performed while the sample is heated from 20°C to 200°C at a rate of 10°C / min. The sample is then held at 200°C for 10 minutes and subsequently cooled from 200°C to 20°C at a rate of 10°C / min.

[0188] After a 10-minute holding period at 20°C, a second ramp-up process heats the temperature from 20°C to 200°C at 10°C / min.

[0189] The glass transition temperature here is the mean glass transition temperature. Using the DSC curve from the second ramp-up process, as obtained under the measurement conditions described above, the glass transition temperature (Tg) is the temperature at the point where the curve segment for the step change in glass transition temperature intersects the straight line equidistant along the vertical axis to the lines extending the baselines on the low-temperature side and the high-temperature side of the step change.

[0190] If the toner particle was produced in an aqueous medium, for example, a portion is taken as a sample and the DSC measurement is carried out on it after parts other than the toner particle have been washed out and dried. Methods for measuring average circularity

[0191] The average circularity of the toner and toner particles is measured using an “FPIA-3000” (Sysmex Corporation), a flow particle image analyzer, under the measurement and analysis conditions during the calibration work.

[0192] The specific measurement procedure is as follows.

[0193] First, 20 mL of deionized water, from which, for example, solid impurities have been removed, are placed in a glass container. To this, approximately 0.2 mL of a dilution is added as a dispersant. This dilution was prepared by approximately three times (by mass) dilution of "Contaminon N" with deionized water (a 10 wt% aqueous solution of a cleaning agent with a neutral pH of 7 for cleaning precision measuring instruments, containing a non-ionic surfactant, an anionic surfactant, and an organic builder, from Wako Pure Chemical Industries, Ltd.).

[0194] 0.02 g of the sample is added and dispersed for 2 minutes using an ultrasonic disperser to obtain a suitable dispersion for measurement. Cooling is applied as needed during this process, ensuring the dispersion temperature ranges from 10°C to 40°C.

[0195] Using a table-top ultrasonic cleaning / dispersing device with a vibration frequency of 50 kHz and an electrical power of 150 W (e.g. “VS-150” (Velvo-Clear Co., Ltd.)) as an ultrasonic disperser, a certain amount of deionized water is added to the water tank and approximately 2 mL of Contaminon N is added to the water tank.

[0196] For the measurement, the flow particle image analyzer with a “UPlanApro” objective (10X, numerical aperture: 0.40) and the particle shell “PSE-900A” (Sysmex Corporation) for the shell solution are used.

[0197] The dispersion produced according to the above-described procedure is placed in the flow particle image analyzer and 3,000 of the toner particles are measured in HPF measurement mode using the Total Count method.

[0198] The average circularity of the toner or toner particle is determined, with the threshold for binarization in particle analysis set to 85% and the analyzed particle diameter limited to a circle-equivalent diameter of 1.985 µm to less than 39.69 µm.

[0199] In this measurement, an automatic focus point adjustment is performed before the start of the measurement using reference latex particles (e.g., a dilution with deionized water of "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A", Duke Scientific Corporation). The focus point is then adjusted every two hours after the start of the measurement.

[0200] Method for measuring the number-averaged particle diameter of primary particles of fine particles of a polyvalent acid metal salt

[0201] The number-averaged particle diameter of the primary particles of a polyvalent metal salt is measured using a scanning electron microscope "S-4800" (product name, by Hitachi, Ltd.). Toner containing added polyvalent metal salt particles is observed, and the principal axis of 100 randomly selected primary particles of the external additive is measured in a field with a maximum magnification of 50,000. The observation magnification is adjusted according to the size of the polyvalent metal salt particles.

[0202] Methods for measuring the normalized intensity of silicon ions present on the toner particle surface

[0203] The normalized intensity of silicon ions at the toner particle surface is determined using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). The instrument used and the measurement conditions are as follows.

[0204] The measurement is performed in toner from which an external additive, such as the fine particle of a polyvalent acid metal salt, has been removed according to the procedure described below. - Measuring device: nanoTOFII (product name, by Ulvac-Phi, Inc.) - Primary ion types: With a 3++ - Acceleration voltage: 30 kV - Primary ion current strength: 0.05 pA - Repetition rate: 8.2 kHz - Grid mode: unmunch - Grid size: 100 µm×100 µm - Measurement mode: positive - Neutralizing electron gun: used - Measurement time: 600 seconds - Rehearsal preparation: Toner particles fixed to an indium plate - Sample pretreatment: no

[0205] The evaluation is performed using the mass numbers of the Si ions and the fragment ions originating from the resin or silane compound, using the standard software ULVAC-PHI (TOF-DR).

[0206] The normalized intensity of the silicon ion (m / z 28) can be derived by dividing the ion intensity derived from silicon (m / z 28) with a mass number of 28 by the total ion intensity of the mass numbers from 1 to 1850.

[0207] The fact that the normalized intensity of the silicon ion (m / z 28) originates from a condensation product of an organosilicon compound is explained here by a 29 Si NMR measurement (solid state) confirmed the following. In a case where the toner particle contains a silicon compound other than a condensation product of an organosilicon compound, the content ratio of the condensation product of an organosilicon compound to the silicon compound contained in the toner particle is determined based on a 29 The intensity is determined by Si-NMR measurement (solid state). The value obtained by multiplying the normalized intensity of the silicon ion (m / z 28) by its concentration ratio is then considered the intensity resulting from the condensation product of an organosilicon compound.

[0208] Method for measuring the normalized intensity of the silicon ions present in the toner particle

[0209] Normally, TOF-SIMS is a surface analysis method where the data in the depth direction provide information for approximately 1 nm. Therefore, the intensity inside the toner is determined after sputtering the toner with an argon gas cluster ion beam (Ar-GCIB) and ablating the surface.

[0210] After sputtering the toner particle under the following conditions, a normalized intensity of the silicon ions (m / z 28), measured according to the same conditions as in “Method for measuring the normalized intensity of the silicon ions present on the toner particle surface” above, is used as the value of the normalized intensity of the silicon ions present inside the toner particle.

[0211] The sputtering conditions are as follows. Acceleration voltage: 5 kV Current: 6.5 nA Grid size: 600×600 µm Irradiation time: 5 seconds / cycle Sputtering time: 250 seconds

[0212] Previously, a PMMA film was sputtered under the same conditions and the cutting depth was checked; it was found that a depth of 80 nm was cut in 250 s.

[0213] Removal of fine particles of a polyvalent acid metal salt and the external additive

[0214] 160 g of sucrose (from Kishida Chemical Co. Ltd.) are added to 100 mL of ion-exchanged water and dissolved in a hot water bath under warming to produce a sucrose concentrate. Then, 31 g of this sucrose concentrate and 6 mL of Contaminon N (a 10 wt% aqueous solution of a pH-7 neutral cleaning agent for precision instruments, containing a non-ionic surfactant, an anionic surfactant, and an organic builder, from Wako Pure Chemical Industries, Ltd.) are added to a centrifuge tube to create a dispersion. Finally, 1 g of toner is added to this dispersion, and any toner lumps are broken up with a spatula or similar tool.

[0215] The centrifuge tube is shaken in a shaker (“KM Shaker” by Iwaki Industry Co., Ltd.) for 30 minutes at 350 strokes per minute. After shaking, the resulting solution is transferred to a 50 mL glass tube for tiltrotors and incubated for 30 minutes under conditions of 58.33 S -1 The sample was centrifuged using a centrifuge (H-9R, from Kokusan Co. Ltd.). After centrifugation, the toner particles were located in the uppermost layer of the glass tube, and an external additive, such as fine particles of a polyvalent acid metal salt, was found on the aqueous solution side in the lower layer.

[0216] The toner particles in the top layer are collected, filtered and washed with 2 L of ion-exchanged water heated to 40°C, and the washed toner particles are recovered.

[0217] Methods for measuring number-averaged molecular weight (Mn) and weight-averaged molecular weight (Mw)

[0218] The number-averaged molecular weight (Mn) and the weight-averaged molecular weight (Mw) of the polymer, resin and toner particle are measured by gel permeation chromatography (GPC) as follows.

[0219] First, a sample to be measured is dissolved in tetrahydrofuran (THF) for 24 hours at room temperature. The resulting solution is then filtered through a solvent-resistant membrane filter, "MYSYORI DISC" (from Tosoh Corporation), with a pore diameter of 0.2 µm to obtain a sample solution. The sample solution is adjusted so that the concentration of the THF-soluble component is approximately 0.8 wt%. A measurement is then performed with the sample solution under the following conditions. Device: HLC8120 GPC (Detector: RI) (by Tosoh Corporation) Column: 7 columns Shodex KF-801, 802, 803, 804, 805, 806, 807 (by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Oven temperature: 40.0°C Sample injection volume: 0.10 mL

[0220] To calculate the molecular weight of the sample, a molecular weight calibration curve is used, which was created using a standard polystyrene resin (product name “TSK STANDARD POLYSTYRENE F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000 or A-500”, from Tosoh Corporation). Method for extracting the silane-modified resin R from the toner particle

[0221] The silane-modified resin R in the toner particle is obtained by separating an extraction product in tetrahydrofuran (THF) according to a solvent gradient elution process. The manufacturing process is as follows.

[0222] For this purpose, 10.0 g of a toner particle are weighed, placed in a cylindrical filter paper (No. 84, from Toyo Roshi Kaisha, Ltd.), and placed in a Soxhlet extractor. The solid obtained by 20-hour extraction with 200 mL of THF as solvent and removal of the solvent from the resulting extract is a THF-soluble substance. This THF-soluble substance contains the silane-modified resin R. The above process is repeated several times to obtain the required amount of THF-soluble substance.

[0223] Preparative gradient HPLC (LC-20AP high-pressure gradient preparation system from Shimadzu Corporation, preparative SunFire column 50 mmφ 250 mm from Waters Co., Ltd.) is used for the solvent gradient elution method. The column temperature is 30°C, the flow rate is 50 mL / min, acetonitrile is used as a poor solvent for the mobile phase, and THF is used as a good solvent. A solution obtained by dissolving 0.02 g of the THF-soluble substance obtained from the extraction in 1.5 mL of THF is used as the separation sample.

[0224] The mobile phase begins with a composition of 100% acetonitrile, and after 5 minutes from sample injection, the THF content is increased by 4% every minute, until the mobile phase composition reaches 100% THF over 25 minutes. The components can be separated by drying the resulting fraction. Resin R can be obtained as a result. The specific component of the fraction that is resin R can be determined by measuring the silicon content and the method described below. 13 C-NMR measurement will be determined. Determination of the structure of the condensation product of an organosilicon compound

[0225] The functional groups contained in the condensation product of an organosilicon compound and the structures of the polymer segment P 1 and the L 1 -segments and the R 1 - to R 3 -Segments in the structure represented by formula (1) were by 1H-NMR analysis, 13 C-NMR analysis, 29 determined by Si NMR analysis and FT-IR analysis.

[0226] If the condensation product of an organosilicon compound is a silane-modified resin R, the synthesized silane-modified resin R or the silane-modified resin R extracted from the toner particle according to the extraction procedure described above is used as the measurement sample. In a case where the condensation product of an organosilicon compound is a condensation product of a silane coupling agent, a THF-insoluble substance from the toner particle is used.

[0227] In a case where the silicon atom is attached to an alkoxy group or hydroxy group under R 1 to R 3 in the structure represented by formula (1), the valence of the alkoxy group or hydroxy group with respect to the silicon atom can be determined according to the formula shown in „29Si-NMR (solid state) measurement conditions” are determined using the methods shown below.

[0228] 29 Si-NMR (solid state) measurement conditions Device: JNM-ECX500II from JEOL RESONANCE Co, Ltd. Sample tube: 3.2 mmφ Sample quantity: 150 mg Measurement temperature: Room temperature Pulse mode: CP / MAS Measured nucleus frequency: 97.38 MHz ( 29 Si) Reference substance: DSS (external standard: 1.534 ppm) Sample rotation speed: 10 kHz Contact time: 10 ms Delay time: 2 s Number of scans: 2000 to 8000

[0229] As a result of the above measurement, a frequency ratio can be determined by peak separation / integration through curve fitting of a plurality of silane components according to the number of oxygen atoms bonded to Si. In this way, the valence of the alkoxy or hydroxy group in the R can be determined. 1to R 3 the resin represented by formula (1) relative to the silicon atoms can be determined.

[0230] A compound with at least one of the following structures—an M-unit, a D-unit, or a T-unit—can be considered a condensation product of an organosilicon compound. A compound with a Q-unit structure can be considered a silicon compound that is not a condensation product of an organosilicon compound.

[0231] In the following structures, at least one of R in each unit is a carbon atom. The other R is an arbitrary group; for example, the other R represents a hydrogen atom, a halogen atom, an alkyl group with one or more carbon atoms, an alkoxy group with one or more carbon atoms, an aryl group with six or more carbon atoms, or a hydroxyl group, similar to R. 1 to R 3 in formula (1).

[0232] The structures of P 1 , L 1 and R 1 to R 3 in the silane-modified resin R represented by formula (1) can be based on a 13 The values ​​are determined by C-NMR measurement (solid state). The measurement conditions are as follows. 13 C-NMR (solid state) measurement conditions Device: JNM-ECX500II from JEOL RESONANCE Co, Ltd. Sample tube: 3.2 mmφ Sample quantity: 150 mg Measurement temperature: Room temperature Pulse mode: CP / MAS Measured nucleus frequency: 123.25 MHz ( 13 C) Reference substance: Adamantane (external standard: 29.5 ppm) Sample rotation speed: 20 kHz Contact time: 2 ms Delay time: 2 s Number of scans: 1024

[0233] Different peaks are identified according to the types of P 1 , L 1 and R 1 to R 3in formula (1) separated, and the peaks are identified to determine the types of P 1 , L 1 and R 1 to R 3 to determine.

[0234] Measurement of the polymerization conversion ratio of polymerizable monomers

[0235] The polymerization conversion ratio of a polymerizable monomer can be measured by gas chromatography (GC) as follows.

[0236] 2.55 mg of DMF (dimethylformamide) are added to 100 mL of acetone to prepare an internal standard solvent. Subsequently, 0.2 g of a dispersion of a polymerizable monomer composition is precisely weighed, and a 10 mL solution is prepared with the aforementioned solvent. The solution is shaken in an ultrasonic shaker for 30 minutes and then allowed to stand for 1 hour. The solution is then filtered through a 0.5 µm membrane filter, and 4 µL of the resulting filtrate is analyzed by gas chromatography.

[0237] First, a calibration curve is generated and the mass-area ratio of a polymerizable monomer and the internal standard DMF is determined. The amount of unreacted polymerizable monomer is calculated from the resulting chromatogram to determine the polymerization conversion ratio.

[0238] The measuring instrument and the measuring conditions are as follows. GC: GC-14A from Shimadzu Corporation Column: J&W Scientific, Inc., DB-WAX (249 µm×0.25 µm×30 m) Carrier gas: N2 Oven: (1) Hold at 70°C for 2 minutes; (2) Heat to 220°C at 5°C / minute Injection opening: 200°C Division ratio: 1:20 Detector: 200°C (FID) Measurement of the total content of Ca and Mg elements in the toner particle

[0239] The total content of Ca and Mg elements originating from the dispersion medium or the like is quantified using an inductively coupled plasma atomic emission spectrometer (ICP-AES (from Seiko Instruments Inc.)).

[0240] As a pretreatment, acid decomposition is carried out with 8.00 mL of 60% nitric acid (Kanto Chemical Co., Inc.; for atomic absorption spectroscopy) in 100.0 mg of toner particles.

[0241] Acid decomposition involves treatment in a sealed container at an internal temperature of 220°C for 1 hour using a microwave high-performance sample pretreatment device ETHOS 1600 (from Milestone Srl) to prepare a solution sample containing multivalent metal elements.

[0242] Ultrapure water is then added to bring the total volume to 50.00 g and obtain a measurement sample. A calibration curve is created for each multivalent metal element, and the amount of metal in each sample is quantified. Additionally, 8.00 mL of nitric acid is made up to a total volume of 50.00 g with ultrapure water, and the resulting solution is measured as a blank; the amount of metal in the blank is then subtracted. Examples

[0243] The present invention is explained in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless expressly stated otherwise, the term "parts" in all cases refers to the mass basis. Production example of resin R1

[0244] The following materials were placed in an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas inlet device, a temperature measuring device and a stirring device, and the reaction was carried out at 200°C for 20 hours in a nitrogen atmosphere at normal pressure. - Alcohol component: 80.9 pieces (2.0 mol adduct of bisphenol A-propylene oxide) - Acid component 1 (terephthalic acid): 16.1 pieces - Acid component 2 (isophthalic acid): 16.1 pieces - Tetrabutoxytitanate: 0.2 parts The following materials were then added, and the reaction was allowed to run for 3 hours at 220°C. - Acid or alcohol component 3 (trimellitic acid): 0.4 parts - Tetrabutoxytitanate: 0.3 parts

[0245] The reaction was continued for 2 hours under reduced pressure in the range of 10 to 20 mmHg. The resulting resin was dissolved in chloroform, and the solution was added dropwise to ethanol, precipitated again, and filtered to obtain a polyester resin.

[0246] The carboxyl group in the obtained polyester resin and the amino group in an aminosilane were amidated as follows to produce the resin R1.

[0247] In this process, 100 parts of the aforementioned polyester were dissolved in 400 parts of N,N-dimethylacetamide, and the following materials were added while stirring for 5 hours at room temperature. After completion of the reaction, this solution was added dropwise to methanol, precipitated again, and filtered to obtain resin R1. - Silane compound (3-aminopropyltrimethoxysilane): 0.2 parts - Triethylamine: 0.3 parts - Condensing agent (amidating agent): 0.3 parts

[0248] [DMT-MM: 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]

[0249] Table 1 lists the structure and physical properties of the obtained resin R1. Production example of resin R2

[0250] The following materials were placed in an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas inlet device, a temperature measuring device and a stirring device, and the reaction was carried out at 200°C for 5 hours in a nitrogen atmosphere at normal pressure. - Alcohol component: (2.0 mol adduct of bisphenol A-propylene oxide) 93.2 pieces - Acid component 1 (terephthalic acid): 11.2 pieces - Acid component 2 (isophthalic acid): 11.2 pieces - Tetrabutoxytitanate: 0.2 parts

[0251] Then the following materials were added and the reaction was continued for 3 hours at 220°C. - Tetrabutoxytitanate: 0.3 parts

[0252] The reaction pressure, reaction temperature and reaction time were adjusted accordingly to obtain a product with a lower molecular weight.

[0253] The carboxyl group of the obtained polyester and the amino group of an aminosilane were amidated as follows to produce the resin R2.

[0254] For this purpose, 100 parts of the aforementioned polyester were dissolved in 400 parts of N,N-dimethylacetamide, and the following materials were added while stirring for 5 hours at room temperature. After completion of the reaction, the resulting solution was added dropwise to methanol, precipitated again, and filtered to obtain resin R2. - Silane compound (3-Aminopropylmethyldimethoxysilane): 1.2 parts - Triethylamine: 2.4 parts - Condensing agent (amidating agent): 2.4 parts [DMT-MM: 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]

[0255] Table 1 lists the structure and physical properties of the resulting resin R2. Production example of resins R3 to R5 and of resin R7

[0256] Resins R3 to R5 and resin R7 were obtained in the same way as in the manufacturing example of resin R2, except that the silane compound, the triethylamine and the condensing agent in the manufacturing example of resin R2 were changed as shown in Table 1.

[0257] Table 1 lists the structure and physical properties of the resins obtained. Production example of resin R6

[0258] In this process, 100 parts of propylene glycol monomethyl ether were heated under nitrogen purge and kept under reflux at a liquid temperature of 120°C or higher. Then, a mixture of the following substances was added dropwise over 3 hours. - Styrene: 64.1 parts - Butyl acrylate: 30.9 parts - Acrylic acid: 5.0 parts - tert-Butyl peroxybenzoate: 1.0 part (Organic polymerization initiator based on peroxide, from NOF Corporation, product name: Perbutyl Z)

[0259] After the dropwise addition was complete, the solution was stirred for 3 hours and then distilled at atmospheric temperature while the liquid temperature was raised to 170°C. Once the liquid temperature reached 170°C, the pressure was reduced to 1 hPa and distillation continued for 1 hour to remove the solvent and obtain a solid resin product. The solid resin product was dissolved in tetrahydrofuran and precipitated with n-hexane; the precipitated solid was then filtered off to obtain a styrene-acrylic resin.

[0260] The carboxyl group in the obtained styrene acrylic resin and the amino group in an aminosilane were amidated as follows to produce the resin R6.

[0261] For this purpose, 100 parts of the aforementioned styrene-acrylic acid copolymer were dissolved in 400 parts of N,N-dimethylacetamide, and the following materials were added while stirring for 5 hours at room temperature. After completion of the reaction, this solution was added dropwise to methanol, precipitated again, and filtered to obtain resin R6. - Silane compound (3-aminopropyltrimethylsilane): 1.0 part - Triethylamine: 2.7 parts - Condensant: 2.7 parts

[0262] [DMT-MM: 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride]

[0263] Table 1 lists the structure and physical properties of the obtained resin R6. [Table 1] Table 1 Resin type Start-Harz Modified silane compound Triethylamine (parts) Condensing agent DMTMM (parts) Properties of silane-modified resin Polymer segment P1 Silane compound starting material Number of parts R 1 R 2 R 3 L 1 Mw R1 BPA(PO)+TPA / IPA 3-Aminopropyltrimethoxysilane 0,2 0,3 0,3 -OMe -OMe -OMe -CONHR 5 - 99651 R2 BPA(PO)+TPA / IPA 3-Aminopropylmethyldimethoxysilane 1,2 2,4 2,4 -OMe -OMe -Me -CONHR 5 - 20036 R3 BPA(PO)+TPA / IPA 3-Aminopropyldimethylmethoxysilane 1,1 2,4 2,4 -OMe -Me -Me -CONHR 5 - 20082 R4 BPA(PO)+TPA / IPA 3-Aminopropyltrimethoxysilane 1,3 2,4 2,4 -OMe -OMe -OMe -CONHR 5 - 20164 R5 BPA(PO)+TPA / IPA 3-Aminopropyltriethoxysilane 1,6 2,5 2,5 -OEt -OEt -OEt -CONHR 5 - 20117 R6 St / BA / AA 3-Aminopropyltrimethylsilane 1,0 2,7 2,7 -Me -Me -Me -CONHR 5 - 18111 R7 BPA(PO)+TPA / IPA 3-Aminopropyltrimethylsilane 1,0 1,0 2,3 -Me -Me -Me -CONHR 5 - 20052

[0264] In the table, P1, L1 and R1 to R3 correspond to P 1 , L 1 and R 1 to R 3 in formula (1). In the table, R5 corresponds to R 5 in formula (2) and denotes a propyl group. Furthermore, Me denotes a methyl group and Et an ethyl group.

[0265] The abbreviations in the tables are as follows. BPA(PO): 2.0 mol adduct of bisphenol A-propylene oxide TPA: Terephthalic acid IPA: Isophthalic acid St: Styrene BA: Butyl acrylate AA: Acrylic acid Production example of toner particles 1

[0266] Preparation of the polymerizable monomer composition 1 - Styrene 60.0 pieces - CI Pigment Blue 15:3 6.3 pieces

[0267] The above-mentioned materials were placed in an attritor (from Nippon Coke & Engineering Co., Ltd.), and dispersion was carried out for 5.0 hours at 220 rpm using zirconia particles with a diameter of 1.7 mm, after which the zirconia particles were removed to obtain a dye-dispersed solution with a pigment dispersed therein.

[0268] The following materials were then added to the above dye-dispersed solution. - Styrene 15.0 pieces - n-Butyl acrylate 25.0 pieces - Hexanediol diacrylate 0.5 parts - polyester resin 5.0 pieces (Condensation polymerization product of terephthalic acid and a propylene oxide 2-mol adduct of bisphenol A; weight-averaged molecular weight Mw of 10000; acid value of 8.2 mgKOH / g) - Release agent (hydrocarbon wax; melting point: 79°C) 5.0 pieces - Plasticizer (ethylene glycol distearate) 15.0 pieces

[0269] In a dissolution / dispersion step, the above-mentioned materials were then kept warm at 65°C and uniformly dissolved and dispersed using the TK Homomixer at 500 rpm to produce a polymerizable monomer composition. Preparation of the aqueous medium 1

[0270] For this purpose, 11.2 parts of sodium phosphate dodecahydrate were added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept warm at 65°C for 1.0 hour while purged with nitrogen. Stirring was performed at 12,000 rpm using the TK Homomixer (Tokushu Kika Kogyo Co., Ltd.). While continuing to stir, an aqueous solution of calcium chloride, obtained by dissolving 7.4 parts of calcium chloride dihydrate in 10.0 parts of ion-exchanged water, was added all at once to the reaction vessel to prepare an aqueous medium containing a dispersion stabilizer. Subsequently, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, thus preparing aqueous medium 1. Granulation step

[0271] While maintaining the temperature of aqueous medium 1 at 70°C and the rotational speed of the agitator at 12,500 rpm, the polymerizable monomer composition was added to the aqueous medium 1, and 8.0 parts of tert-butyl peroxypivalate were added as a polymerization initiator. Granulation was carried out for 10 minutes while maintaining the rotational speed of 12,500 rpm in the agitator. Polymerization step A

[0272] The high-speed stirrer was modified to a stirrer with a propeller-type stirring blade, and the polymerization was carried out for 5.0 hours at a temperature of 70°C and while stirring at 200 rpm. Polymerization step B

[0273] Following polymerization step A, a polymerization reaction was carried out by further increasing the temperature to 85°C and heating for 2.0 hours. Then, 0.03 parts of 3-methacryloxypropyltrimethoxysilane (M1) were added while stirring for 5 minutes, after which a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.0.

[0274] The residual monomer was removed by increasing the temperature to 98°C and heating for 3.0 hours. The temperature was then lowered to 55°C and maintained at this temperature for 5.0 hours with stirring. Subsequently, the temperature was lowered to 25°C. Ion-exchanged water was added to adjust the concentration of toner particles in the dispersion to 30.0% and to obtain a toner particle dispersion 1 in which toner particles 1 are dispersed. Washing step

[0275] The toner particle dispersion 1 was adjusted to a pH of 1.5 with 1 mol / L hydrochloric acid under stirring for 1.0 hour, then filtered under washing with ion-exchanged water and dried to obtain toner particles 1.

[0276] The silane compounds used are listed in Table 2, and the physical properties of the resulting toner particle 1 are given in Table 3. Production example of toner particles 2

[0277] Toner particle 2 was then produced in the same way as in the production example of toner particle 1, except that the amount of 3-methacryloxypropyltrimethoxysilane (M1) added in the production example of toner particle 1 was changed to 0.01 parts.

[0278] The silane compounds used are listed in Table 2, and the physical properties of the resulting toner particle 2 are given in Table 3. Production example of toner particles 3

[0279] A mixed solution of 15.0 parts ion-exchanged water, the pH of which had been adjusted to 4.0 by the addition of 1 mol / L hydrochloric acid, and 0.15 parts 3-methacryloxypropyltrimethoxysilane (M1) was mixed using a stirrer until a uniform phase was formed, giving the monomer hydrolysis solution 1.

[0280] Toner particle 3 was then obtained in the same way as in the preparation example of toner particle 1, except that here, once polymerization step A in the preparation example of toner particle 1 was completed, the entire amount of monomer hydrolysis solution 1 was added while stirring for 5 minutes, followed by adjusting the pH to 9.0 by adding a 1 mol / L aqueous sodium hydroxide solution, and except that no 3-methacryloxypropyltrimethoxysilane (M1) was added in polymerization step B.

[0281] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 3 are given in Table 3. Production example of toner particles 4

[0282] Toner particle 4 was then obtained in the same way as in the preparation example of toner particle 1, except that here, after polymerization step A in the preparation example of toner particle 1 was completed, 0.15 parts of 3-methacryloxypropyltrimethoxysilane (M1) were added while stirring for 5 minutes, followed by adjusting the pH to 9.0 by adding a 1 mol / L aqueous sodium hydroxide solution, and except that no 3-methacryloxypropyltrimethoxysilane (M1) was added in polymerization step B.

[0283] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 4 are given in Table 3. Production example of toner particles 5

[0284] A mixed solution of 0.03 parts ion-exchanged water, the pH of which had been adjusted to 4.0 by the addition of 1 mol / L hydrochloric acid, and 0.02 parts methyltrimethoxysilane (M7) was mixed using a stirrer until a uniform phase was formed, giving rise to the monomer hydrolysis solution 2.

[0285] Toner particle 5 was then obtained in the same way as in the production example of toner particle 2, except that here the entire amount of monomer hydrolysis solution 2 was added immediately after lowering the temperature to 55°C in the production example of toner particle 2.

[0286] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 5 are given in Table 3. Production example of toner particles 6

[0287] Toner particle 6 was then obtained in the same way as in the preparation example of toner particle 1, except that here 0.01 parts of 3-methacryloxypropyltrimethoxysilane (M1) in the preparation example of toner particle 1 were changed to 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).

[0288] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 6 are given in Table 3. Production example of toner particles 7

[0289] Toner particle 7 was then obtained in the same way as in the preparation example of toner particle 6, except that after the addition of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) in the preparation example of toner particle 6, the stirring time until the pH value was adjusted to 9.0 was changed to 60 minutes.

[0290] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 7 are given in Table 3. Production example of toner particles 8

[0291] Toner particle 8 was then prepared in the same manner as in the preparation example of toner particle 6, except that the addition of 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) in the preparation example of toner particle 6 was modified after lowering the temperature to 55°C in polymerization step B, and except that this addition was followed by 60 minutes of stirring and subsequent addition of a 1 mol / L aqueous solution of sodium hydroxide to adjust the pH to 9.0, with the temperature of 55°C then being maintained for 4.0 hours while stirring was continued.

[0292] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 8 are given in Table 3. Production example of toner particles 9 to 12

[0293] Toner particles 9 to 12 were prepared in the same manner as in the preparation example of toner particle 1, except that 3-methacryloxypropyltrimethoxysilane (M1) in the preparation example of toner particle 1 was modified as shown in Table 3.

[0294] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 9 to 12 are given in Table 3. Production example of toner particles 13 Preparation of the aqueous medium 2

[0295] For this purpose, 10.2 parts of magnesium chloride were added to a reaction vessel containing 250.0 parts of ion-exchanged water, and the mixture was kept warm at 65°C for 1.0 hour with nitrogen purging. Stirring was performed at 12,000 rpm using the TK Homomixer (Tokushu Kika Kogyo Co., Ltd.). While continuing to stir, an aqueous solution of calcium chloride, obtained by dissolving 6.2 parts of calcium chloride in 50.0 parts of ion-exchanged water, was added all at once to the reaction vessel to prepare an aqueous medium containing a dispersion stabilizer. Subsequently, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 6.0, thus preparing aqueous medium 2.

[0296] Subsequently, toner particle 13 was obtained in the same way as in the production example of toner particle 1, except that here the aqueous medium 1 in the production example of toner particle 1 was changed to aqueous medium 2.

[0297] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 13 are given in Table 3. Production example of toner particles 14

[0298] Toner particle 14 was obtained in the same manner as toner particle 13, except that the amount of magnesium chloride in the preparation example for toner particle 13 was changed to 12.2 parts. Table 3 lists the physical properties of the obtained toner particle 14. Production example of toner particles 15

[0299] Toner particle 15 was then obtained in the same manner as in the preparation example for toner particle 1, except that the 5.0 parts polyester resin in the preparation example for toner particle 1 were changed to 4.5 parts polyester resin and 1.00 part resin R1. Table 3 lists the physical properties of the obtained toner particle 15. Production example of toner particles 16 to 21 and 25

[0300] Toner particles 16 to 21 and 25 were obtained in the same manner as in the preparation example for toner particle 15, except that the resin R1 in the preparation example for toner particle 15 was modified by one of the resins R2 to R7 in the amount specified in Table 3. Table 3 lists the physical properties of the obtained toner particles 16 to 21 and 25. Production example of toner particles 22 Production of a binder resin particle dispersion

[0301] 89.5 parts styrene, 9.2 parts butyl acrylate, 1.3 parts acrylic acid (as the carboxyl group-donating monomer), and 3.2 parts n-lauryl mercaptan were mixed and dissolved. An aqueous solution obtained by dissolving 1.5 parts Neogen RK (from DKS Co., Ltd.) in 150 parts ion-exchanged water was added to the above solution with dispersion.

[0302] An aqueous solution, obtained by dissolving 0.3 parts potassium persulfate in 10 parts ion-exchanged water, was added with slow stirring for 10 minutes. After nitrogen exchange, emulsion polymerization was carried out at 70°C for 6 hours. Upon completion of polymerization, the reaction solution was cooled to room temperature and ion-exchanged water was added to obtain a binder-resin particle dispersion with a solids concentration of 12.5 wt% and a volume-based mean particle size of 0.2 µm.

[0303] The binder resin that formed the resin particles had a carboxyl group derived from acrylic acid. The glass transition temperature of the binder resin was 57°C. Production of a wax dispersion

[0304] In this process, 100 parts of a diester compound (ethylene glycol distearate), 30 parts of paraffin wax "HNP-9" (from Nippon Seiro Co., Ltd.; melting point 75°C) as a release wax, and 20 parts of Neogen RK were mixed with 400 parts of ion-exchanged water. The resulting mixture was then dispersed for approximately one hour using a JN 100 wet jet mill (from Jokoh Co., Ltd.) to obtain a wax dispersion. Preparation of a dye-dispersed solution

[0305] CI Pigment Blue 15:3 (100 parts) was mixed as a dye and 15 parts Neogen RK with 885 parts ion-exchanged water, and the resulting mixture was dispersed for about 1 hour using a JN 100 wet jet mill to obtain a dye-dispersed solution.

[0306] Subsequently, 265 parts of the obtained binder resin particle dispersion, 80 parts of the wax dispersion, and 10 parts of the dye dispersion solution were dispersed using a homogenizer (Ultra-Turrax T50, from IKA KK). The temperature in the vessel was adjusted to 30°C while stirring, and the pH was adjusted to 8.0 by adding a 1 mol / L aqueous sodium hydroxide solution.

[0307] An aqueous solution, resulting from dissolving 0.5 parts magnesium chloride in 10 parts ion-exchanged water, was added as a flocculant over 10 minutes at 30°C with stirring. After a 3-minute stand, heating was initiated and the temperature increased to 50°C to generate aggregated particles. In this state, the particle diameter of the aggregated particles was measured using the Coulter Counter Multisizer 3 (registered trademark of Beckman Coulter Inc.). When the weight-averaged particle diameter reached 6.5 µm, 3.0 parts sodium chloride and 8.0 parts Neogen RK were added to stop particle growth.

[0308] The particles were then heated to 95°C and stirred continuously at this temperature to induce melt adhesion and spherification of the aggregated particles. Once the average circularity reached 0.980, the particles were cooled to 80°C and maintained at this temperature. Ice water was then added to cool from a starting temperature of 80°C to a final temperature of 30°C at a rate of 3°C / sec.

[0309] The temperature was then increased to 55°C by adding 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) and stirring for 60 minutes. The pH was then adjusted to 9.0 by adding a 1 mol / L aqueous sodium hydroxide solution, and the temperature was maintained at 55°C for 4.0 hours while stirring, followed by cooling to 25°C to obtain the toner particle dispersion 22.

[0310] The pH of the obtained toner particle dispersion 22 was adjusted to a pH of 1.5 with 1 mol / L hydrochloric acid under stirring for 1.0 hour, then filtered under washing with ion-exchanged water and dried to obtain toner particles 22.

[0311] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 22 are given in Table 3. Production example of toner particles 23 - Binder resin (styrene-n-butyl acrylate copolymer):n-butyl acrylate copolymerization ratio (mass ratio) of 75:25, peak molecular weight (Mp) of 22,000, weight-averaged tesar weight (Mw) of 35,000, Mw / Mn = 2.4, where Mn represents the determined molecular weight. 100.0 pieces - CI Pigment Blue 15:3 6.3 pieces - Release agent (hydrocarbon wax; melting point 759°C) 5.0 pieces - Plasticizer (ethylene glycol distearate) 5.0 pieces

[0312] The materials mentioned above were premixed using an FM mixer (from Nippon Coke & Engineering Co., Ltd.) and then melt-kneaded using a twin-screw kneading extruder (PCM-30, from Ikegai Corp.) to obtain a kneaded product. The resulting kneaded product was cooled, coarsely pulverized using a hammer mill (Hosokawa Micron Corporation), and then finely pulverized using a mechanical pulverizer (T-250, Turbo Kogyo Co., Ltd.) to obtain a finely pulverized powder.

[0313] The resulting finely pulverized powder was resuspended in aqueous medium 1 to obtain a new dispersion, whereupon the temperature was again increased to 55°C. Subsequently, 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) were added and the mixture was stirred for 60 minutes. The pH was then adjusted to 9.0 by adding a 1 mol / L aqueous sodium hydroxide solution, and the temperature was maintained at 55°C for 4.0 hours with stirring, followed by cooling to 25°C to obtain the toner particle dispersion 23.

[0314] The pH of the obtained toner particle dispersion 23 was adjusted to a pH of 1.5 with 1 mol / L hydrochloric acid under stirring for 1.0 hour, then filtered under washing with ion-exchanged water and dried to obtain toner particles 23.

[0315] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 23 are given in Table 3. Production example of toner particles 24

[0316] Toner particle 24 was obtained in the same way as in the preparation example of toner particle 3, except that 3-methacryloxypropyltrimethoxysilane (M1) in the preparation example of toner particle 3 was changed to 0.50 parts.

[0317] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 24 are given in Table 3. Production example of toner particles 26

[0318] The toner particle 26 was obtained in the same way as in the preparation example of toner particle 1, except that no 3-methacryloxypropyltrimethoxysilane (M1) was added in polymerization step B of the preparation example of toner particle 1.

[0319] The physical properties of the obtained toner particles 26 are listed in Table 3. The normalized intensity of toner particle 26 in Table 3 is a numerical value derived from the base intensity. Production example of toner particles 27

[0320] Toner particle 27 was then obtained in the same way as in the preparation example of toner particle 24, except that the 3-methacryloxypropyltrimethoxysilane (M1) in the preparation example of toner particle 24 was changed to 0.40 parts 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).

[0321] The silane compounds used are listed in Table 2, and the physical properties of the obtained toner particles 27 are given in Table 3. Production example of toner particles 28

[0322] Toner particle 28 was then obtained in the same way as in the preparation example of toner particle 1, except that 0.03 parts silicon dioxide particles (Snowtex PS (from Nissan Chemical Corporation)) were added during the preparation of the polymerizable monomer composition 1 in the preparation example of toner particle 1, and except that no 3-methacryloxypropyltrimethoxysilane (M1) was added in polymerization step B.

[0323] The physical properties of the obtained toner particle 28 are listed in Table 3. [Table 2] Table 2 Monomer type Silane compound starting material M1 3-Methacryloxypropyltrimethoxysilane M2 3-Methacryloxypropyltris(trimethylsiloxy)silane M3 3-Methacryloxypropylmethyldimethoxysilane M4 3-Methacryloxyoctyltrimethoxysilane M5 3-Methacryloxypropyltriethoxysilane M6 3-Acryloxypropyltrimethoxysilane M7 Methyltrimethoxysilane [Table 3] Table 3 Toner particle no. Si source Number of parts Si source addition step Waiting time until pH increases after adding Si source Conversion ratio of Si source (from reaction step further) (%) D4 Average circularity Tg Metal originating from the dispersant Amount of metal originating from the dispersant µmol / g Presence / absence of condensation Normalized intensity of silicon ions Si source 1 Si-Source2 Si-Source1 (parts) Si-Source2 (parts) *1 *2 1 M1 - 0,03 - Polymerization step B 5 min 98,9 6,5 µm 0,982 55°C Approx 4,0 Available 2,11.E-03 5,49.E-04 2 M1 - 0,01 - Polymerization step B 5 min 99,1 6,4 µm 0,983 55°C Approx 4,3 Available 7,17.E-04 5,10.E-04 3 M1 - 0,15 - Polymerization step A 5 min 97,9 6,7 µm 0,978 55°C Approx 4,4 Available 2,04.E-02 4,51.E-04 4 M1 - 0,15 - Polymerization step A 5 min 97,3 6,7 µm 0,977 55°C Approx 4,0 Available 2,61.E-03 2,30.E-04 5 M1 M7 0,01 0,02 Polymerization step B 5 min 99,1 6,4 µm 0,985 55°C Approx 4,2 Available 1,52.E-03 4,10.E-04 6 M2 - 0,40 - Polymerization step B 5 min 99,2 6,5 µm 0,985 55°C Approx 4,1 Available 8,20.E-04 2,08.E-04 7 M2 - 0,40 - Polymerization step B 60 min 99,0 6,4 µm 0,981 55°C Approx 4,0 Available 6,81.E-03 6,87.E-04 8 M2 - 0,40 - After reducing the temperature to 55°C 60 min 99,9 6,4 µm 0,984 55°C Approx 4,5 Available 1,68.E-02 6,10.E-04 9 M3 - 0,03 - Polymerization step B 5 min 99,1 6,6 µm 0,981 55°C Approx 4,4 Available 1,06.E-03 4,27.E-04 10 M4 - 0,03 - Polymerization step B 5 min 99,2 6,5 µm 0,983 55°C Approx 4,0 Available 8,62.E-04 5,53.E-04 11 M5 - 0,03 - Polymerization step B 5 min 98,9 6,7 µm 0,982 55°C Approx 4,3 Available 1,93.E-03 4,34.E-04 12 M6 - 0,03 - Polymerization step B 5 min 98,9 6,7 µm 0,982 55°C Approx 4,1 Available 2,04.E-03 4,93.E-04 13 M1 - 0,03 - Polymerization step B 5 min 99,2 6,6 µm 0,981 55°C Mg 20,0 Available 2,42.E-03 5,06.E-04 14 M1 - 0,03 - Polymerization step B 5 min 99,1 6,5 µm 0,982 55°C Mg 24,0 Available 2,42.E-03 5,06.E-04 15 Harz R1 - 1,00 - Dissolution / dispersion step - - 6,8 µm 0,980 56°C Approx 4,5 Available 7,16.E-04 6,83.E-04 16 Harz R2 - 0,50 - Dissolution / dispersion step - - 6,8 µm 0,983 55°C Approx 4,0 Available 1,56.E-03 5,81.E-04 17 Harz R3 - 0,50 - Dissolution / dispersion step - - 6,7 µm 0,982 55°C Approx 4,3 Available 1,18.E-03 6,13.E-04 18 Harz R4 - 0,50 - Dissolution / dispersion step - - 6,7 µm 0,984 55°C Approx 4,6 Available 1,67.E-03 5,93.E-04 19 Harz R5 - 0,50 - Dissolution / dispersion step - - 6,6 µm 0,984 56°C Approx 4,1 Available 1,85.E-03 6,02.E-04 20 Harz R6 - 0,50 - Dissolution / dispersion step - - 6,6 µm 0,983 55°C Approx 4,2 Available 1,54.E-03 5,61.E-04 21 Harz R7 - 0,50 - Dissolution / dispersion step - - 6,5 µm 0,982 55°C Approx 4,2 Available 1,94.E-03 5,88.E-04 22 M2 - 0,40 - After raising the temperature to 55°C 60 min 99,9 6,5 µm 0,981 56°C Mg 4,5 Available 1,68.E-03 6,10.E-04 23 M2 - 0,40 - After raising the temperature to 55°C 60 min 99,9 6,3 µm 0,949 57°C Approx 4,5 Available 1,68.E-03 6,10.E-04 24 M1 - 0,50 - Polymerization step A 5 min 97,9 6,5 µm 0,977 55°C Approx 4,5 Available 6,26.E-02 6,90.E-04 25 Harz R1 - 3,00 - Dissolution / dispersion step - - 6,6 µm 0,983 55°C Approx 4,4 Available 6,07.E-02 1,16.E-03 26 - - - - None - - 6,6 µm 0,985 55°C Approx 4,0 Absent 2,10.E-04 2,42.E-04 27 M2 - 0,40 - Polymerization step ① 5 min 97,9 6,6 µm 0,979 55°C Approx 4,3 Available 1,53.E-03 7,93.E-04 28 silicon dioxide particles - 0,03 - None - - 6,7 µm 0,977 57°C Approx 4,1 Absent 1,52.E-04 7,98.E-05

[0324] In the tables, *1 denotes the normalized intensity of silicon ions (m / z 28) in a time-of-flight secondary ion mass spectrometer (TOF-SIMS) for the respective toner particle. Furthermore, *2 denotes the normalized intensity of silicon ions (m / z 28) after sputtering the toner particle under the above condition (A).

[0325] The label “Presence / Absence of Condensation” indicates whether the toner particle contains a condensation product of an organosilicon compound or not.

[0326] In terms of normalized intensity, the specification "2.11.E-03" here means, for example, "2.11 × 10 -3 “. Production example of toner 1 Production of a toner particle dispersion

[0327] Toner particle 1 was resuspended with ion-exchanged water to obtain a toner particle dispersion 1 with a toner particle concentration of 20 mass-%. Addition of fine particles of a polyvalent metal salt

[0328] The materials listed below were weighed into a reaction vessel and mixed using a propeller stirrer. Sodium phosphate (dodecahydrate) 0.9 parts Titanium lactate (TC-310, from Matsumoto Fine Chemical Co., Ltd.) 1.0 parts Toner particle dispersion 1 500.0 pieces

[0329] The pH of the resulting mixed solution was then adjusted to 7.0 and the temperature of the mixed solution to 55°C, after which the mixed solution was held for one hour and mixed with a propeller stirrer.

[0330] The pH was then adjusted to 9.5 using an aqueous solution of 1 mol / L NaOH, and the temperature was kept at 50°C for 2 hours while stirring.

[0331] The pH was then adjusted to 1.5 with 1 mol / L hydrochloric acid while stirring for 1 hour, subsequently filtered and dried while washing with ion-exchanged water, after which the resulting finely pulverized powder was classified using a multi-stage classifier according to the Coanda effect to obtain toner 1.

[0332] In an SEM observation, the number-averaged particle diameter of a titanium phosphate compound was 11 nm. A calculation of the abundance of the titanium phosphate compound using X-ray fluorescence yielded a result of 0.2 parts per 100 toner particles.

[0333] Table 4 lists the physical properties of the obtained toner 1.

[0334] Production example of toner 2 to 5, 9 to 18, 21 to 31, 35 to 37, 39 and 40

[0335] Toners 2 to 5, 9 to 18, 21 to 31, 35 to 37, 39, and 40 were obtained in the same manner as in the preparation example for toner 1, except that the type of toner particles, the number of parts of the polyvalent acid source, and the type and number of parts of the metal source were changed as shown in Table 4 in the preparation example for toner 1. The amount of fine particles of a polyvalent acid metal salt on the surface of each obtained toner was as shown in Table 4.

[0336] Table 4 lists the physical properties of the toners obtained. Production example of toner 6

[0337] Toner 6 was obtained by adding 0.5 parts of titanium oxide particles as a metal source to 100.0 parts of toner particles 1, the whole being mixed with an FM mixer (from Nippon Coke & Engineering Co., Ltd.).

[0338] Table 4 lists the physical properties of the obtained toner 6. Manufacturing example of toners 7, 8, 32, 33 and 38

[0339] Toners 7, 8, 32, 33 and 38 were obtained in the same manner as in the manufacturing example of toner 6, except that the type and number of toner particles and the metal source were changed as shown in Table 4.

[0340] Table 4 lists the physical properties of the toners obtained. Production example of toner 19 Ion-exchanged water 100.0 pieces Sodium sulfate 4.8 pieces

[0341] The above-mentioned components were mixed, and then 10.0 parts of titanium lactate (TC-310, from Matsumoto Fine Chemical Co., Ltd.) were added while stirring at 13,000 rpm using the TK Homomixer (from Tokushu Kika Kogyo Co., Ltd.) at room temperature. The pH was adjusted to 7.0 by adding 1 mol / L hydrochloric acid.

[0342] A solid fraction was then obtained by centrifugation. The process of redispersing in ion-exchanged water and obtaining the solid fraction by centrifugation was then repeated three times to remove ions such as sodium. The resulting product was again dispersed in ion-exchanged water and dried by spray drying to obtain titanium sulfate compound particles 1 with a number-averaged particle diameter of 99 nm.

[0343] Then 0.5 parts of the titanium sulfate compound fine particles 1 were added to 100.0 parts of toner particles 1, and the whole thing was mixed with an FM mixer (from Nippon Coke & Engineering Co., Ltd.) to obtain toner 19.

[0344] Table 4 lists the physical properties of the obtained toner 19. Production example of toner 20 Ion-exchanged water 100.0 pieces Sodium carbonate 3.6 pieces

[0345] The above-mentioned components were mixed, and then 10.0 parts of titanium lactate (TC-310, from Matsumoto Fine Chemical Co., Ltd.) were added while stirring at 13,000 rpm using the TK Homomixer (from Tokushu Kika Kogyo Co., Ltd.) at room temperature. The pH was adjusted to 7.0 by adding 1 mol / L hydrochloric acid.

[0346] The solid fraction was then recovered by centrifugation. The process of redispersing in ion-exchanged water and recovering the solid fraction by centrifugation was then repeated three times to remove ions such as sodium. The resulting product was again dispersed in ion-exchanged water and dried by spray drying to obtain titanium carbonate compound particles 1 with a number-averaged particle diameter of 91 nm.

[0347] Then 0.5 parts of the titanium carbonate compound fine particles 1 were added to 100.0 parts of toner particles 1, and the whole thing was mixed with an FM mixer (from Nippon Coke & Engineering Co., Ltd.) to obtain toner 20.

[0348] Table 4 lists the physical properties of the obtained toner 20. Production example of toner 34

[0349] In this process, 0.5 parts silicon dioxide were added to 100.0 parts toner particles 1 and the whole thing was mixed with an FM mixer (from Nippon Coke & Engineering Co., Ltd.) to obtain toner 34. [Table 4] Table 4 Toner No. toner particles Source of polyhydric acid Metal source DA(nm) X (parts) Art Number of parts Art Number of parts 1 Toner particles 1 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 11 0,2 2 Toner particles 2 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 12 0,2 3 Toner particles 3 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 12 0,2 4 Toner particles 4 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 15 0,2 5 Toner particles 1 Sodium phosphate (dodecahvdrate) 0,9 Aluminum lactate 1,6 22 0,2 6 Toner particles 1 - - titanium oxide 0,5 28 0,5 7 Toner particles 1 - - Aluminum oxide 0,5 15 0,5 8 Toner particles 1 - - Strontium titanate 0,5 15 0,5 9 Toner particles 5 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 13 0,2 10 Toner particles 6 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 12 0,2 11 Toner particles 7 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 11 0,2 12 Toner particles 8 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 13 0,2 13 Toner particles 9 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 16 0,2 14 Toner particles 10 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 16 0,2 15 Toner particles 11 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 15 0,2 16 Toner particles 12 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 12 0,2 17 Toner particles 13 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 11 0,2 18 Toner particles 14 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 14 0,2 19 Toner particles 1 Sodium sulfate - titanium lactate - 99 0,5 20 Toner particles 1 Sodium carbonate - titanium lactate - 91 0,5 21 Toner particles 15 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 13 0,2 22 Toner particles 16 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 12 0,2 23 Toner particles 17 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 11 0,2 24 Toner particles 18 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 14 0,2 25 Toner particles 19 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 12 0,2 26 Toner particles 20 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 12 0,2 27 Toner particles 21 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 11 0,2 28 Toner particles 22 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 13 0,2 29 Toner particles 23 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 11 0,2 30 Toner particles 1 Sodium phosphate (dodecahvdrate) 0,2 titanium lactate 0,3 7 0,1 31 Toner particles 1 Sodium phosphate dodecahydrate 18,0 titanium lactate 10,0 183 2,8 32 Toner particles 1 - - titanium oxide 0,1 28 0,1 33 Toner particles 1 - - titanium oxide 5,0 28 0,5 34 Toner particles 1 - - - - - - 35 Toner particles 24 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 14 0,2 36 Toner particles 25 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 13 0,2 37 Toner particles 26 Sodium phosphate (dodecahvdrate) 0,9 titanium lactate 1,0 13 0,2 38 Toner particles 26 - - titanium oxide 0,5 28 0,5 39 Toner particles 27 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 14 0,2 40 Toner particles 28 Sodium phosphate dodecahydrate 0,9 titanium lactate 1,0 14 0,2

[0350] In the table, DA denotes the number-averaged particle diameter of the fine particles of a polyvalent acid metal salt. Furthermore, X denotes the quantity of fine particles of a polyvalent acid metal salt per 100 parts of toner particles. Reference example 1

[0351] First, an electrophotographic device in the form of a modified Canon Inc. LBP652C laser printer was prepared. The printer was modified so that it could be connected to an external high-voltage power supply and provide an arbitrary potential difference between a loading blade and a loading roller; in addition, the process speed was set to 200 mm / s.

[0352] Next, a process cartridge filled with toner 1 was used as a cartridge for LBP652C and the electrophotographic device was left for 48 hours in an environment with normal temperature and humidity (25°C / 50%RH) to acclimate to the measurement environment. Assessment of load retention capacity

[0353] First, the potential difference between the loading blade and loading roller was set to -400 V, and a completely black image was printed. The printer was stopped during image generation, the process cartridge was removed from the housing, and the charge of the toner on the photosensitive drum was evaluated using the E-SPART Analyzer EST-1 charge distribution meter (from Hosokawa Micron Corporation).

[0354] The charge retention capability was assessed by comparing the charge quantity on a developing roller in the above assessment of charge injection capability with the charge quantity on the photosensitive drum in the present assessment.

[0355] In this assessment, the higher the charge retention capacity, the less likely charge leakage becomes during a development step, thus ensuring a greater charge quantity is retained. In other words, the lower the numerical value, the better the charge retention capacity.

[0356] The evaluation results for reference example 1 are listed in Table 5. Load retention capacity A: Difference between the charge quantity on the developing roller and on the photosensitive drum of 3 µC / g or less B: Difference between the charge on the developing roller and on the photosensitive drum of more than 3 µC / g and up to 6 µC / g C: Difference between the charge on the developing roller and on the photosensitive drum of more than 6 µC / g and up to 10 µC / g D: Difference between the charge quantity on the developing roller and on the photosensitive drum of more than 10 µC / g Charge injection capability (injection charge quantity)

[0357] First, the potential difference between the loading blade and the loading roller was set to 0 V, and a pure white image was printed. The printer was stopped during image generation, the process cartridge was removed from the housing, and the charge quantity and charge distribution of the toner on the developing roller were evaluated using the E-SPART Analyzer EST-1 charge distribution meter (from Hosokawa Micron Corporation).

[0358] Subsequently, the potential difference between the charging blade and the charging roller was set to -400 V and the same evaluation was carried out.

[0359] An injection charge quantity and an injection charge quantity distribution were evaluated based on the change ΔQ / M (units µC / g) of the charge quantity and the change in the charge quantity distribution at a potential difference of 0 V and -400 V.

[0360] The evaluation criterion for the charge quantity distribution was by what multiple the half-value width of a charge quantity distribution for -400 V is greater than the half-value width of the charge quantity distribution for 0 V.

[0361] According to this criterion, a smaller multiple means a sharper charge distribution and a better state of charge.

[0362] In the present evaluation, the higher the charge injection capability, the greater the change in charge quantity for a given potential difference, and consequently, the greater the charge quantity difference (ΔQ / M). Simultaneously, it becomes possible to achieve a uniform charge quantity distribution, which is a property of the superior injection charge.

[0363] The results of the evaluation of reference example 1 are shown in Table 5. Charge injection capability A: ΔQ / M of more than 20 µC / g B: ΔQ / M of more than 10 µC / g and up to 20 µC / g C: ΔQ / M of more than 5 µC / g and up to 10 µC / g D: ΔQ / M of 5 µC / g or less Injection charge quantity distribution A: The half-width of the charge quantity distribution for -400 V is 0.70 times or less than that for 0 V B: The half-width of the charge quantity distribution for -400 V is more than 0.70 times and up to 0.80 times that for 0 V C: The half-width of the charge quantity distribution for -400 V is more than 0.80 times and up to 0.90 times greater than that for 0 V D: The half-width of the charge quantity distribution for -400 V is more than 0.90 times greater than that for 0 V Evaluation of charge injection capability (injection charge quantity) at low voltage

[0364] An evaluation was carried out under similar conditions to the above evaluation of the charge injection capability, except that the potential difference between the charging blade and the charging roller was changed to -200 V.

[0365] The injection charge quantity and the injection charge quantity distribution were evaluated based on the change ΔQ / M (units µC / g) of the charge quantity and the change in the charge quantity distribution at a potential difference of 0 V and -200 V.

[0366] In the present assessment, the greater the difference ΔQ / M (unit µC / g) in the amount of charge between potential differences of 0 V and -200 V, the better the charge injection capability and the higher the amount of charge even at low voltage.

[0367] The results of the evaluation of reference example 1 are shown in Table 5. Low-voltage charge injection capability A: ΔQ / M of more than 20 µC / g B: ΔQ / M of more than 10 µC / g and up to 20 µC / g C: ΔQ / M of more than 5 µC / g and up to 10 µC / g D: ΔQ / M of 5 µC / g or less

[0368] Reference examples 2 to 20 and 28 to 40, examples 21 to 27 and comparative examples 1 to 6

[0369] The evaluations were performed in the same manner as in Reference Example 1, except that the filler toner was changed as specified in Table 5. The evaluation results are shown in Table 5. [Table 5] Table 5 Toner No. Load retention capacity Injection charge quantity (400V) Injection charge quantity distribution Injection charge quantity (200V) Charge quantity difference (µC / g) Evaluation Charge quantity at 400 V (µC / g) ΔQ / M(µC / g) Evaluation Half-width (multiple) Evaluation Charge quantity at 200 V (µC / g) ΔQ / M'(µC / g) Evaluation Example 1 1 1 A -46 25 A 0,67 A -40 19 B Example 2 2 1 A -40 18 B 0,79 B -34 12 B Example 3 3 6 B -45 23 A 0,69 A -39 17 B Example 4 4 1 A -45 25 A 0,69 A -39 19 B Example 5 5 2 A -41 23 A 0,76 B -35 17 B Example 6 6 3 A -36 21 A 0,76 B -30 15 B Example 7 7 3 A -38 22 A 0,79 B -31 15 B Example 8 8 2 A -38 22 A 0,79 B -30 14 B Example 9 9 1 A -49 28 A 0,65 A -44 23 A Example 10 10 2 A -41 19 B 0,77 B -33 11 B Example 11 11 4 B -44 24 A 0,65 A -38 18 B Example 12 12 6 B -42 23 A 0,65 A -39 20 B Example 13 13 2 A -46 23 A 0,69 A -40 17 B Example 14 14 1 A -46 22 A 0,69 A -39 15 B Example 15 15 3 A -47 25 A 0,67 A -41 19 B Example 16 16 3 A -47 24 A 0,70 A -42 19 B Example 17 17 6 B -45 24 A 0,78 B -38 17 B Example 18 18 7 C -43 21 A 0,85 C -35 13 B Example 19 19 2 A -38 17 B 0,74 B -32 11 B Example 20 20 2 A -35 16 B 0,72 B -30 11 B Example 21 21 2 A -40 18 B 0,79 B -36 14 B Example 22 22 2 A -52 26 A 0,69 A -46 20 B Example 23 23 3 A -53 27 A 0,70 A -47 21 A Example 24 24 1 A -53 29 A 0,65 A -49 25 A Example 25 25 1 A -52 29 A 0,68 A -48 23 A Example 26 26 1 A -54 28 A 0,69 A -48 22 A Example 27 27 2 A -56 29 A 0,69 A -52 25 A Example 28 28 5 B -45 23 A 0,68 A -41 19 B Example 29 29 6 B -41 23 A 0,67 A -35 17 B Example 30 30 2 A -46 22 A 0,78 B -42 18 B Example 31 31 6 B -42 23 A 0,68 A -35 16 B Example 32 32 2 A -46 25 A 0,79 B -39 18 B Example 33 33 6 B -44 24 A 0,69 A -39 19 B Comparative example 1 34 4 B -33 3 D 0,91 D -31 1 D Comparative example 2 35 13 D -51 26 A 0,88 C -44 19 B Comparative example 3 36 15 D -56 31 A 0,72 B -52 27 A Comparative example 4 37 5 B -37 9 C 0,73 B -30 2 D Comparative example 5 38 4 B -31 4 D 0,98 D -29 2 D Comparative example 6 39 12 D -46 25 A 0,65 A -40 19 B Comparative example 7 40 9 C -30 3 D 0,91 D -40 1 D

[0370] While the present invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments.

Claims

[1] Toner comprising a toner particle containing a binder resin, wherein the toner particle comprises a condensation product of an organosilicon compound, in time-of-flight secondary ion mass spectrometry (TOF-SIMS) of the toner particle, a normalized intensity of silicon ions (m / z 28) originating from the condensation product of the organosilicon compound, given by the following expression (I), of 7.00×10 -4 up to 3.00×10 -2 amounts; normalized intensity of silicon ions (m / z28) = {ion intensity (m / z 28) of silicon ions} / {gemation intensity from m / z 0.5 to 1850} a normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles with an Ar-gas cluster ion beam Ar-GCIB under the following condition (A) 6.99×10 -4 or less; (A) Acceleration voltage: 5 kV, Current: 6.5 nA, Grid size: 600×600 µm, Irradiation time: 5 seconds / cycle, Sputtering time: 250 seconds, the toner contains fine particles on the surface of the toner particles, and The fine particles of a polyvalent acid metal salt are a reaction product of a compound comprising at least one of the elements Ti and Al, and a polyvalent acid. wherein the condensation product of the organosilicon compound is a silane-modified resin R with the structure represented by the following formula (1); in formula (1) P 1 represents a styrene-acrylic resin segment or a polyester resin segment; L 1 represents a single bond or a divalent compound group; R 1 to R 3Each independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 or more carbon atoms, an alkoxy group with 1 or more carbon atoms, an aryl group with 6 or more carbon atoms, or a hydroxy group; and m represents a positive integer; in a case where m is equal to or greater than 2, a plurality of L 1 , a plurality of R 1 , a plurality of R 2 and a plurality of R 3 each may be identical or different; however, Si is bonded to at least one carbon, and at least one of R 1 to R 3 is condensed with an organosilicon compound. [2] Toner according to claim 1, where the normalized intensity of the silicon ions (m / z 28) of the toner particle is 7.00×10 -4 up to 8.00×10 -3 is, and the normalized intensity of the silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles under condition (A) 6.00×10 -4 or less. [3] Toner according to claim 1 or 2, wherein the polyvalent acid of the fine particles of a polyvalent acid metal salt is phosphoric acid. [4] Toner according to any one of claims 1 to 3, wherein a metal element in the fine particles is a polyvalent acid metal salt Ti. [5] Toner according to any one of claims 1 to 4, wherein the total content of Ca and Mg elements in the toner particle is 23 µmol / g or less, as measured by an inductively coupled plasma atomic emission spectrometer. [6] Toner according to any one of claims 1 to 5, wherein at least one of the residues R 1 to R 3 represents an alkoxy group with 1 or more carbon atoms or a hydroxy group. [7] Toner according to any one of claims 1 to 5, wherein the groups in R 1 to R 3 , which are not condensed with the organosilicon compound, each independently represent an alkoxy group with 1 or more carbon atoms or a hydroxy group. [8] Toner according to any one of claims 1 to 7, wherein L 1 represented by the following formula (2); in formula (2) R represents 5 a single bond, an alkylene group, or an arylene group; * represents a bond segment at P 1 of formula (1); and ** represents a bond segment to the silicon atom in formula (1). [9] Toner according to any one of claims 1 to 8, wherein the fine particle content is from 0.10 parts by mass to 0.30 parts by mass, based on 100 parts by mass of the toner particle. [10] Toner according to any one of claims 1 to 9, wherein a number-averaged particle diameter DA of the fine particles a polyvalent acid metal salt from 5 nm to 30 nm.