Toner

Abstract

The present invention relates to a toner. A toner includes toner particles containing a binder resin, wherein the toner particles contain a condensation product of an organic silicon compound, and in a time-of-flight secondary ion mass spectrum of the toner particles, a normalized intensity of silicon ions derived from the condensation product of the organic silicon compound is 7.00×10 ‑4 Above and 3.00×10 ‑2 The normalized intensity of silicon ions after sputtering toner particles under specific conditions is 6.99×10 ‑4 Hereinafter, the toner includes fine particles on the surfaces of the toner particles, and the fine particles have at least one selected from the group consisting of specific polyacid metal salt fine particles, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

Description

Technical Field

[0001] The present disclosure relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, or a toner jet system recording method. Background Art

[0002] Methods of visualizing image information through electrostatic latent images, such as electrophotography, have been employed in copying machines, multifunction devices, and printers; in recent years, further demands have been placed on such methods in terms of achieving cost reduction and image quality improvement.

[0003] In this case, toners are required to faithfully reproduce the latent image. To ensure faithful reproduction of the latent image, precise control of toner charge is effective. Insufficient control of toner charge leads to defects such as fogging, in which low-charged toner develops in non-image areas, and poor control, in which excessively charged toner fuses to the toner carrying member, which are factors that hinder faithful reproduction of the latent image.

[0004] Hitherto, as a toner charging method, triboelectric charging in which electric charge is imparted to the toner by friction between the toner and a carrier or a charging member (hereinafter collectively referred to as a charging member) has been widely studied.

[0005] However, because friction between the charging member and the toner does not occur uniformly, triboelectric charging produces overcharged toner and undercharged toner. This occurs because the charge generated by triboelectric charging is generated only in those areas where the toner and the charging member are in contact.

[0006] Furthermore, triboelectric charging is highly susceptible to humidity, with the charge amount varying between low-humidity and high-humidity environments. Furthermore, triboelectric charging is significantly affected by the fluidity of the toner. When the toner deteriorates, for example due to long-term use, the fluidity decreases, causing the charge amount to vary.

[0007] In order to solve these problems in the triboelectric charging process, research on an injection charging process has been conducted. The injection charging process is a process in which toner is charged by injecting electric charges due to a potential difference between the toner and a charging member.

[0008] In this case, if conductive paths exist in the toner and between the toners, the entire toner can be uniformly charged, rather than charging only those regions that are in contact with the charging member.

[0009] Furthermore, since the charge amount can be arbitrarily controlled by changing the potential difference when injection charging is present, the charge amount required by the system can be easily met. Furthermore, since injection charging is resistant to the influence of humidity, changes in charge amount caused by the environment can be suppressed.

[0010] However, the problem with injection charging is that it is difficult to achieve coexistence between charge injection and charge retention. This occurs because the presence of conductive paths within the toner and between toners makes it easy for the injected charge to leak out, resulting in a trade-off between charge injection capability and charge retention capability.

[0011] Japanese Patent Application Laid-Open No. 2005-148409 discloses a toner whose volume resistivity is reduced at high voltage, and discloses an injection charging process using this toner. The process described in this patent document aims to eliminate the trade-off between charge injectability and charge retention by subjecting the toner to a charge injection process alone at a high voltage that reduces the toner's volume resistivity.

[0012] From another point of view, Japanese Patent Application Laid-Open No. 2019-133145 discloses a toner in which the surface of the toner base particles is coated with metal fine particles and an organic silicon compound to achieve both control of charging characteristics and durability. Summary of the Invention

[0013] Japanese Patent Application Publication No. 2005-148409 states that precise control of the charge amount is problematic because high voltage is required to achieve injection charging through the charge injection process, which promotes discharge. Furthermore, since other processes must be completed at lower voltages, the design freedom of voltage setting for this process is limited.

[0014] The toner disclosed in Japanese Patent Application Publication No. 2019-133145 exhibits excellent charge-rise performance during conventional friction charging, while the toner is less likely to cause member contamination and has excellent durability.

[0015] On the other hand, there are few means of injecting charge into toner base particles, so the charge tends to be retained on the surface of the toner particles. Consequently, the charge tends to leak through the fine metal particles on the toner particle surface, resulting in insufficient charge retention. Therefore, improvements are needed to be implemented in the injection charging process.

[0016] In light of the foregoing, a toner that achieves a high degree of compatibility between charge injectability and charge retainability during injection charging has not yet been obtained, and further improvement is desired.

[0017] The present disclosure provides a toner capable of precise charging control and having the ability to achieve high image quality by providing coexistence between charge injectability and charge retainability during injection charging.

[0018] The present disclosure relates to a toner comprising toner particles containing a binder resin,

[0019] wherein the toner particles comprise a condensation product of an organosilicon compound,

[0020] In time-of-flight secondary ion mass spectrometry TOF-SIMS of toner particles,

[0021] The normalized intensity of silicon ions (m / z 28) given by the following formula (I) derived from the condensation product of the organosilicon compound was 7.00×10 -4 Above and 3.00×10 -2 the following;

[0022] Normalized intensity of silicon ion (m / z 28) = {ionic intensity of silicon ion (m / z 28)} / {total ionic intensity of m / z 0.5 to 1850} (I),

[0023] The normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles by Ar gas cluster ion beam Ar-GCIB under the following conditions (A) was 6.99×10 -4 the following;

[0024] (A) Acceleration voltage: 5 kV, current: 6.5 nA, grating size: 600 × 600 μm, irradiation time: 5 sec / cycle, sputtering time: 250 sec,

[0025] The toner includes fine particles on the surface of the toner particles, and

[0026] The fine particles have at least one selected from the group consisting of polyacid metal salt fine particles which are reaction products of a compound containing at least one of Ti and Al elements and a polyacid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

[0027] The present disclosure provides a toner capable of precise charging control and having the ability to achieve high image quality by providing coexistence between charge injectability and charge retainability during injection charging.

[0028] Further features of the present invention will become apparent from the following description of exemplary embodiments. DETAILED DESCRIPTION

[0029] Unless otherwise specified, in the present invention, the description of a numerical range such as “XX or more and YY or less” or “XX to YY” includes the numerical values of the upper limit and the lower limit of the numerical range.

[0030] When a numerical range is described in steps, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0031] In order for a toner to exhibit a high degree of suitability for injection charging, it is important that the transfer of charge should occur only during the injection charging process, and that the transfer of charge should not occur in any other process. The present inventors have speculated that in order for a toner to exhibit the above-mentioned characteristics, it is necessary that charge can be injected not only near the toner surface but also inside the toner during the injection charging process, and that leakage of charge from near the toner surface is less likely to occur in processes other than the injection charging process.

[0032] As a result of intensive studies, the present inventors have found that a toner having the following configuration can achieve both injection of charge and retention of charge in the injection charging process.

[0033] In other words, the present disclosure relates to a toner including toner particles containing a binder resin,

[0034] wherein the toner particles comprise a condensation product of an organosilicon compound,

[0035] In time-of-flight secondary ion mass spectrometry TOF-SIMS of toner particles,

[0036] The normalized intensity of the silicon ion (m / z 28) given by the following formula (I) derived from the condensation product of the organosilicon compound is 7.00×10 -4 Above and 3.00×10 -2 the following;

[0037] Normalized intensity of silicon ion (m / z 28) = {ionic intensity of silicon ion (m / z 28)} / {total ionic intensity of m / z 0.5 to 1850} (I),

[0038] The normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles by Ar gas cluster ion beam Ar-GCIB under the following conditions (A) was 6.99×10 -4 the following;

[0039] (A) Acceleration voltage: 5 kV, current: 6.5 nA, grating size: 600 × 600 μm, irradiation time: 5 sec / cycle, sputtering time: 250 sec,

[0040] The toner includes fine particles on the surface of the toner particles, and

[0041] The fine particles have at least one selected from the group consisting of polyacid metal salt fine particles which are reaction products of a compound containing at least one of Ti and Al elements and a polyacid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

[0042] The present inventors believe that the underlying mechanism is as follows.

[0043] In the above-mentioned toner composition, when charges are injected during the injection charging process, the metal-containing fine particles with excellent conductivity present on the toner quickly receive a large amount of charges, and thereafter the charges migrate to the condensation products of the organic silicon compound having a silyl group on the surface of the toner particles, which tend to become negatively charged.

[0044] In this case, the metal-containing fine particles become excessively charged during the process of intentionally applying a large amount of charge, such as during injection charging. As a result, it is believed that charge is also easily supplied to the condensation product of the organosilicon compound that is near the metal-containing fine particles but not in contact with the metal-containing fine particles. Therefore, even if a small amount of the condensation product of the organosilicon compound is used, a charging effect can be expected.

[0045] Furthermore, the condensation product of the organosilicon compound interacts with the binder resin, promoting the transfer of charge to the toner. This series of flows allows charge to be uniformly and rapidly injected from the metal-containing fine particles into the toner via the small amount of the condensation product of the organosilicon compound present near the toner particle surface, thereby achieving high charge injection properties.

[0046] At the same time, it is believed that after undergoing the injection charging process, the highly conductive metal-containing fine particles become the starting point for charge leakage. By limiting the condensation product of the organosilicon compound, which easily mediates charge transfer, to only a very small amount near the toner particle surface, it becomes possible to minimize the transfer of charge from the toner interior to the toner surface, as well as the transfer of charge caused by contact between the condensation product of the organosilicon compound and the metal-containing fine particles.

[0047] That is, leakage of charge from the inside of the toner can be suppressed, and high charge retention can be achieved.

[0048] The toner will be described based on the above-mentioned mechanism.

[0049] Examples of condensation products of organosilicon compounds include condensation products of organosilicon compounds such as silane coupling agents; silane-modified resins obtained by reaction with silane coupling agents or hydrosilanes; polymers of organosilane compounds or hybrid resins thereof; and condensation products of the above. Preferred herein are condensation products of silane coupling agents and silane-modified resins R having a structure represented by the following formula (1):

[0050] As the silane coupling agent, known organic silicon compounds can be used without particular limitation, and specific examples thereof include the following bifunctional silane compounds having two functional groups and trifunctional silane compounds having three functional groups.

[0051] Examples of the bifunctional silane compound include dimethyldimethoxysilane and dimethyldiethoxysilane.

[0052] Examples of the trifunctional silane compound include the following.

[0053] trifunctional silane compounds having an alkyl group as a substituent, such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, and decyltriethoxysilane;

[0054] trifunctional silane compounds having an alkenyl group as a substituent, such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and allyltriethoxysilane;

[0055] trifunctional silane compounds having an aromatic group as a substituent, such as phenyltrimethoxysilane and phenyltriethoxysilane;

[0056] trifunctional silane compounds having a methacryloxyalkyl group as a substituent, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane, and 3-methacryloxypropyltris(trimethylsiloxy)silane; and

[0057] For example, trifunctional silane compounds having an acryloxyalkyl group as a substituent, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, and γ-acryloxypropylethoxydimethoxysilane.

[0058] The condensation product of the organosilicon compound is more preferably a silane-modified resin R having a structure represented by the following formula (1). When the toner particles have the silane-modified resin R which is a condensation product of the organosilicon compound, the propagation efficiency of the charge to the inside of the toner particles is improved and the charge amount is further increased.

[0059]

[0060] In the above formula (1), P 1 Indicates the polymer part; L 1 Represents a single bond or a divalent linking group; R 1 to R 3 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxyl group; m represents a positive integer; when m is equal to or greater than 2, multiple L 1 , multiple R 1 , multiple R 2 and multiple R 3 However, Si is bonded to at least one carbon and R 1 to R 3 At least one of them is condensed with the organosilicon compound.

[0061] In R 1 to R 3 When at least one of them is condensed with an organosilicon compound, the group condensed with the organosilicon compound has an -O-Si≡ structure.

[0062] In the above formula (1), R 1 to R 3 Among them, preferably, at least one represents an alkoxy group having 1 or more carbon atoms, or a hydroxyl group. More preferably, R 1 to R 3 The groups that do not condense with the organosilicon compound each independently represent an alkoxy group having 1 or more carbon atoms or a hydroxyl group.

[0063] In the above substituents, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 4. The alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 4, even more preferably 1 to 3, particularly preferably 1 or 2. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms.

[0064] The content of silicon atoms in the resin R is preferably from 0.02% by mass to 10.00% by mass. The content is more preferably from 0.10% by mass to 5.00% by mass, and still more preferably from 0.50% by mass to 2.00% by mass.

[0065] The content of the resin R is preferably 0.10 to 10.00 parts by mass, more preferably 0.20 to 5.0 parts by mass, and still more preferably 0.50 to 2.0 parts by mass relative to 100.0 parts by mass of the binder resin.

[0066] In this paper, the P in formula (1) 1 There are no particular restrictions, and examples thereof include a polyester resin moiety, a vinyl resin moiety, a styrene acrylic resin moiety, a polyurethane resin moiety, a polycarbonate resin moiety, a phenolic resin moiety, and a polyolefin resin moiety.

[0067] Among them, the above P 1 It preferably contains a styrene acrylic resin moiety or a polyester resin moiety. For example, P 1 It can be a hybrid resin portion of a polyester resin and a styrene acrylic resin. More preferably, P 1 With polyester resin part. 1 In the case of the polyester resin portion, the interaction with the binder resin is high, the injection charging performance is further improved, and a high charge amount can be obtained even at a low voltage.

[0068] When MwA represents the weight average molecular weight of the silane-modified resin R having the structure of formula (1), MwA is preferably 8,000 to 50,000. When MwA is 8,000 or greater, the amount of low-molecular-weight components is reduced, and heat-resistant storage properties are easily improved. When MwA is 50,000 or less, the molecular mobility after fixing is high, and spatial alignment is easily achieved; as a result, the adhesiveness to the output paper is easily improved.

[0069] More preferably, MwA is 12000 or more and 30000 or less. MwA can be controlled by changing the reaction temperature, reaction time, monomer composition, initiator amount, and the like of the resin.

[0070] Any method can be adopted as a method for forming the silane-modified resin R having the structure of formula (1); examples thereof include the following methods.

[0071] The silane-modified resin R can be formed by the following methods: a method comprising reacting carboxyl groups in a resin with an aminosilane coupling agent, a method comprising polymerizing an ethylenically unsaturated binding site or a monomer having an ethylenically unsaturated bond in a resin and a (meth)acrylic silane coupling agent, a method comprising reacting hydroxyl groups in a resin with an isocyanate silane coupling agent, and a method comprising reacting isocyanate groups in a resin with an aminosilane coupling agent.

[0072] Examples of the aminosilane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, and 3-aminopropylmethoxydimethylsilane.

[0073] Examples of the (meth)acrylic silane coupling agent 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-(methacryloxy)propyltris(trimethylsiloxy)silane.

[0074] Examples of the isocyanate-based coupling agent include isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane.

[0075] In the silane-modified resin R having the structure of formula (1), P 1 In the case where the structure is a polyester resin moiety, examples of the polycondensation monomer that can be used to prepare the polyester resin moiety include polycarboxylic acids and polyols.

[0076] Examples of the polycarboxylic acid 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, terephthalic acid, isophthalic acid, terephthalic acid, phthalic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0077] Examples of the polycarboxylic acid other than dicarboxylic acids include, for example, trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.

[0078] Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, dipentaerythritol , tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropylene glycol, 2-methyl-1,2,4-butanetriol, isosorbide, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct and hydrogenated bisphenol A propylene oxide adduct.

[0079] The polyester resin is not particularly limited, but is preferably a condensation product of a diol and a dicarboxylic acid. The polyester resin is preferably, for example, a polyester resin having a structure represented by the following formula (6) and at least one structure (a plurality of structures may be selected) selected from the group consisting of the structures represented by the following formulas (7) to (9). Alternatively, the polyester resin may be a polyester resin having a structure represented by the following formula (10).

[0080]

[0081] In formula (6), R 9 represents an alkylene group, an alkenylene group or an arylene group. 10 represents an alkylene group or a phenylene group. In formula (8), R 18 represents an ethylene group or a propylene group. In addition, x and y are integers equal to or greater than 0, such that the average value of x+y is 2 to 10. In formula (10), R 11 represents an alkylene group or an alkenylene group.

[0082] In formula (6), R 9 Examples of the alkylene group (preferably having 1 to 12 carbon atoms) include methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.

[0083] In formula (6), R 9 Examples of the alkenylene group (preferably having 2 to 4 carbon atoms) include ethenylene, propenylene and 2-butenylene.

[0084] In formula (6), R 9Examples of the arylene group (preferably having 6 to 12 carbon atoms) include 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 2,6-naphthylene, 2,7-naphthylene and 4,4′-biphenylene.

[0085] R in formula (6) 9 In this case, examples of the substituent include a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and a combination thereof.

[0086] In formula (7), R 10 Examples of the alkylene group (preferably having 1 to 12 carbon atoms) include methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, and 1,3-cyclopentylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.

[0087] In formula (7), R 10 Examples of the phenylene group include 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene.

[0088] R in formula (7) 10 In this case, examples of the substituent include a methyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a combination thereof.

[0089] In formula (10), R 11 Examples of the alkylene group (preferably having 1 to 12 carbon atoms) include methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene and 1,4-cyclohexylene.

[0090] In formula (10), R 11 Examples of alkenylene groups (preferably having 2 to 40 carbon atoms) include vinylene, propenylene, butenylene, butadienylene, pentenylene, hexenylene, hexadienylene, heptenylene, octenylene, decenylene, octadecenylene, eicosylene and triacontenylene groups. These alkenylene groups can have any one of a straight chain, a branched chain and a cyclic structure. In addition, the double bond can be in any position as long as there is at least one double bond.

[0091] R in formula (10) 11 In this case, examples of the substituent that can be substituted include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a combination thereof.

[0092] In P 1In the case of a styrene acrylic resin or a vinyl resin, the monomer is not particularly limited, and known monomers can be used. For example, the following monomers can be used.

[0093] Such as styrene derivatives such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene and p-phenylstyrene;

[0094] Acrylic acid polymerizable monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl dimethyl phosphate acrylate, ethyl diethyl phosphate acrylate, ethyl dibutyl phosphate acrylate, 2-hydroxyethyl acrylate, and 2-benzoyloxyethyl acrylate; and

[0095] Such as methacrylic acid-based polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl ethyl methacrylate, 2-hydroxyethyl methacrylate and dibutyl ethyl methacrylate.

[0096] It can be obtained from L in formula (1) 1 The divalent linking group represented by is not particularly limited, and examples thereof include structures represented by the following formulae (2) to (5). In these cases, the injection chargeability can be further improved, and a high charge amount can be achieved even at a low voltage. This can be said to be due to the high interaction with the binder resin, which allows the charge to be more smoothly transferred to the P 1 Part.

[0097] The atom of the linking group bonded to Si in formula (1) is preferably a carbon atom.

[0098]

[0099] R in formula (2) 5 represents a single bond, an alkylene group or an arylene group. (*) represents the same as P in formula (1) 1 and (**) represents the bonding site with the silicon atom in formula (1).

[0100] R in formula (3)6 represents a single bond, an alkylene group or an arylene group. (*) represents the same as P in formula (1) 1 and (**) represents the bonding site with the silicon atom in formula (1).

[0101] R in formulas (4) and (5) 7 and R 8 Each independently represents an alkylene group, an arylene group or an oxyalkylene group. (*) represents the same as P in formula (1) 1 and (**) represents the bonding site with the silicon atom in formula (1).

[0102] Among the above, L 1 Preferred is a divalent linking group containing an amide bond represented by the above formula (2).

[0103] The structure represented by formula (2) is a divalent linking group containing an amide bond.

[0104] The linking group can be formed, for example, by reacting carboxyl groups in the resin with aminosilanes.

[0105] There is no particular limitation on aminosilanes, and examples thereof include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β-(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, and 3-aminopropylsilane, etc.

[0106] R 5 The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in is not particularly limited, and may be, for example, an alkylene group containing an -NH- group.

[0107] R 5 The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in is not particularly limited, and may be, for example, an arylene group containing a heteroatom.

[0108] The structure represented by formula (3) is a divalent linking group containing a urethane bond.

[0109] The linking group can be formed, for example, by reacting hydroxyl groups in the resin with an isocyanate silane.

[0110] There are no particular limitations on the isocyanate silane, and examples thereof include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyldimethylethoxysilane.

[0111] R 6 The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in is not particularly limited, and may be, for example, an alkylene group containing an -NH- group.

[0112] R 6 The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in is not particularly limited, and may be, for example, an arylene group containing a heteroatom.

[0113] The structure represented by formula (4) or (5) is a divalent linking group including a bond grafted to an ester bond in the resin.

[0114] The linking group is formed, for example, by an epoxysilane insertion reaction.

[0115] The term "epoxysilane insertion reaction" refers to a reaction that includes the step of inserting the epoxy group of epoxysilane into the ester bond contained in the resin backbone. Furthermore, the term "insertion reaction" as used herein is described in the Journal of Synthetic Organic Chemistry, Japan, Vol. 49, No. 3, p. 218, 1991, as referring to "insertion reaction of an epoxy compound into the ester bond in a polymer chain."

[0116] The reaction mechanism of epoxysilane insertion reaction can be represented by the following model diagram.

[0117]

[0118] In the figure above, D and E represent the constituent parts of the resin, and F represents the constituent part of the epoxy compound.

[0119] Two compounds are formed by α-cleavage and β-cleavage during the ring opening of the epoxy group in the figure. In both cases, a compound in which the epoxy group is inserted into the ester bond in the resin is obtained. In other words, a compound in which the constituent part of the epoxy compound other than the epoxy portion is grafted to the resin is obtained.

[0120] The epoxysilane is not particularly limited, and examples thereof include β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane.

[0121] R 7 and R 8 The alkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in is not particularly limited, and may be, for example, an alkylene group containing an -NH- group.

[0122] R 7 and R 8 The arylene group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms) in is not particularly limited, and may be, for example, an arylene group containing a heteroatom.

[0123] R 7 and R 8 The oxyalkylene group (preferably having 1 to 12 carbon atoms, more preferably 2 to 4 carbon atoms) in is not particularly limited, and may be, for example, an oxyalkylene group containing an -NH- group.

[0124] In the time-of-flight secondary ion mass spectrometry TOF-SIMS of the toner particles, the normalized intensity of silicon ions (m / z 28) given by the expression (I) derived from the condensation product of the organic silicon compound needs to be within 7.00×10 -4 Above and 3.00×10 -2 Within the following range.

[0125] Normalized intensity of silicon ion (m / z 28) = {ionic intensity of silicon ion (m / z 28)} / {total ionic intensity of m / z 0.5 to 1850}...(I)

[0126] When the normalized intensity of silicon ion (m / z 28) is lower than 7.00×10 -4 When the normalized intensity of silicon ions (m / z 28) is higher than 3.00×10 -2 When the charge retention property is not exhibited, it is difficult to achieve both the charge injection property and the charge retention property.

[0127] In order to achieve higher charge retention, the normalized intensity of silicon ions (m / z 28) is more preferably 7.00×10 -4 Above and 8.00×10 -3 Below, still more preferably 8.00×10 -4 Above and 8.00×10 -3 the following.

[0128] The normalized intensity falling within this range indicates that the amount of silicon ions on the surface of the toner particles is much smaller than that in conventional techniques. It is believed that by obtaining a normalized intensity within the above range, it is possible to simultaneously achieve both charge injection and charge retention properties by taking measures such as using a very small amount of an organic silicon compound compared to conventional examples, controlling the hydrolysis of the organic silicon compound, and shortening the condensation time.

[0129] Furthermore, the normalized intensity of silicon ions (m / z 28) by time-of-flight secondary ion mass spectrometry after sputtering the toner particles by Ar gas cluster ion beam Ar-GCIB under the following conditions (A) needs to be 6.99×10 -4 the following.

[0130] (A) Acceleration voltage: 5 kV, current: 6.5 nA, grating size: 600 × 600 μm, irradiation time: 5 sec / cycle, sputtering time: 250 sec

[0131] The silicon ions derived from the condensation product of the organosilicon compound present inside the toner particles can be evaluated by sputtering under condition (A); herein, the less the condensation product of the organosilicon compound inside the toner particles, the more the charge retention is improved. Preferably, the normalized intensity is 6.00×10 -4 The lower limit of the normalized intensity is not particularly limited, but is preferably 1.00×10 -4 More than 2.00×10 -4 above.

[0132] Any method can be employed as a method for obtaining toner particles having a desired normalized intensity of silicon ions (m / z 28). For example, in the case where a silane-modified resin R is used as a condensation product of an organic silicon compound, examples of such methods include a method of adding the resin R during the step of dissolving or dispersing a polymerizable monomer capable of forming a binder resin.

[0133] In the case of using a condensation product of a silane coupling agent as the condensation product of the organosilicon compound, examples include a method in which polycondensation is carried out after appropriately adding a silane coupling agent in the step of dissolving or dispersing a polymerizable monomer, or in the step of obtaining toner particles by polymerization of a polymerizable monomer. Other methods include a method involving adding a silane coupling agent to a toner particle dispersion during polycondensation.

[0134] There is an optimal pH for the polycondensation reaction of the organosilicon compound. Therefore, by performing the polycondensation of the organosilicon compound at the optimal pH value for the polycondensation reaction, the reaction can be efficiently carried out.

[0135] The method of adding the organosilicon compound such as the silane coupling agent may include adding the organosilicon compound as it is, or mixing the organosilicon compound with an aqueous medium in advance and then adding the resulting hydrolyzate.

[0136] Methods for controlling the normalized intensity of silicon ions (m / z 28) near the surface of the toner particles or inside the toner particles may include controlling, for example, the amount of the organic silicon compound added, the polymerization conversion rate of the polymerizable monomer, the hydrolysis time or the polycondensation time after the addition of the organic silicon compound to form a condensation product of the organic silicon compound.

[0137] The toner further comprises fine particles on the surface of the toner particles. The fine particles comprise at least one selected from the group consisting of fine particles of a polyacid metal salt which is a reaction product of a compound containing at least one of Ti and Al elements and a polyacid, fine particles of strontium titanate, fine particles of titanium oxide, and fine particles of aluminum oxide.

[0138] Among these, in consideration of achieving higher injection chargeability of the toner as a whole and achieving further more uniform charging performance, polyacid metal salt fine particles that are reaction products of a polyacid and a compound containing Ti and / or Al are preferred, with Ti being more preferred as the metal element. Even more preferably, the polyacid in the polyacid metal salt fine particles is phosphoric acid, as in this case, the charge amount distribution is further uniform.

[0139] The content of the fine particles is preferably 0.01 parts by mass or more and 5.00 parts by mass or less, more preferably 0.02 parts by mass or more and 3.00 parts by mass or less, and still more preferably 0.10 parts by mass or more and 0.30 parts by mass or less, relative to 100 parts by mass of the toner particles.

[0140] As the polybasic acid, heretofore known polybasic acids can be used without particular limitation.

[0141] The polyacid preferably includes an inorganic acid. Inorganic acids have a more rigid molecular skeleton than organic acids, and therefore, their properties rarely change during long-term storage. Therefore, injection charging properties can be obtained in a stable manner even after long-term storage.

[0142] Specific examples of the polybasic acid include inorganic acids such as phosphoric acid (tribasic), carbonic acid (dibasic), and sulfuric acid (dibasic), and organic acids such as dicarboxylic acid (dibasic) and tricarboxylic acid (tribasic).

[0143] Specific examples of the organic acid include dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid; and tricarboxylic acids such as citric acid, aconitic acid, and trimellitic anhydride.

[0144] Among them, at least one selected from the group consisting of phosphoric acid, carbonic acid, and sulfuric acid as inorganic acids is preferred, and phosphoric acid is particularly preferred.

[0145] Specific examples of the polyacid metal salt include metal phosphates such as titanium phosphate compounds and aluminum phosphate compounds; metal sulfates such as titanium sulfate compounds and aluminum sulfate compounds; metal carbonates such as titanium carbonate compounds and aluminum carbonate compounds; and metal oxalates such as titanium oxalate compounds. Among them, titanium phosphate compounds are preferred.

[0146] The method for obtaining polyacid metal salt fine particles is not particularly limited, and a known method can be employed. Among them, a method comprising reacting polyacid ions with a metal compound constituting a metal source in an aqueous medium to obtain polyacid metal salt fine particles is preferred.

[0147] In the case of obtaining polyacid metal salt fine particles according to the above method, as the metal source, conventionally known metal compounds can be used as long as the metal compound can generate polyacid metal salt by reacting with polyacid ions.

[0148] Specific examples are metal chelates such as titanium lactate, titanium tetraacetylacetonate, titanium ammonium lactate, titanium triethanolamine, zirconium lactate, zirconium ammonium lactate, aluminum lactate, aluminum triacetylacetonate and copper lactate; and metal alkoxides such as titanium tetraisopropoxide, titanium ethoxide, zirconium tetraisopropoxide and aluminum triisopropoxide.

[0149] Among them, metal chelates are preferred because their reaction is easy to control and they react quantitatively with polyacid ions. From the viewpoint of solubility in aqueous media, lactic acid chelates such as titanium lactate and zirconium lactate are more preferred.

[0150] The polyacid ions mentioned above can be used as the polyacid ions. Regarding the form when added to the aqueous medium, the polyacid can be added directly, or a water-soluble polyacid metal salt can be added to the aqueous medium and dissociated in the aqueous medium.

[0151] When the polyacid metal salt fine particles are obtained by the above method, the number average particle diameter DA of the polyacid metal salt fine particles can be controlled by, for example, the reaction temperature and the raw material concentration during the synthesis of the polyacid metal salt fine particles.

[0152] The number average particle diameter DA of the polyacid metal salt fine particles is preferably 3 nm to 100 nm, more preferably 5 nm to 30 nm, still more preferably 8 nm to 20 nm.

[0153] The total content of Ca and Mg elements in the toner particles, as measured by inductively coupled plasma atomic emission spectrometry, is preferably 23 μmol / g or less, more preferably 20 μmol / g or less. The lower limit is not particularly limited, but is preferably 0 μmol / g or more, more preferably 2 μmol / g or more.

[0154] The total content within the above range means that the amount of the metal element constituting the charge leakage source is small near the toner particle surface, thereby improving the charge retention and also making it easier to achieve both the charge retention and injection charging properties.

[0155] When toner particles are produced in an aqueous medium, a calcium compound and / or a magnesium compound may be used as a dispersant. The content can be controlled, for example, based on the amount of these dispersants used and by removing the dispersants by washing the toner particles.

[0156] Method for producing toner particles

[0157] The method for producing toner particles will now be described. Known methods such as kneading and pulverization or wet production methods can be employed. Wet production methods are preferred from the perspectives of achieving uniform particle size and shape controllability. Examples of wet production methods include suspension polymerization, dissolution suspension, emulsion polymerization, and emulsion aggregation. Among these, suspension polymerization is preferably employed.

[0158] Next, a method of producing toner particles according to the suspension polymerization method will be described.

[0159] First, a polymerizable monomer capable of generating a binder resin and various materials as needed are mixed and a polymerizable monomer composition in which the above materials are dissolved or dispersed is prepared using a disperser.

[0160] Examples of the above-mentioned various materials include a colorant, a wax release agent, a charge control agent, a polymerization initiator, a chain transfer agent, and the like.

[0161] Examples of the disperser include a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser.

[0162] Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles to prepare droplets of the polymerizable monomer composition using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser (granulation step).

[0163] Thereafter, the polymerizable monomer in the liquid droplets of the polymerizable monomer composition is polymerized to produce toner particles (polymerization step).

[0164] The polymerization initiator may be mixed during the preparation of the polymerizable monomer composition, or may be mixed into the polymerizable monomer composition immediately before droplets are formed in the aqueous medium.

[0165] Furthermore, a polymerization initiator may be optionally added in a state of being dissolved in a polymerizable monomer or other solvent during granulation into droplets or after completion of granulation, that is, immediately before the start of the polymerization reaction.

[0166] Once the resin particles are obtained by polymerization of the polymerizable monomer, a solvent removal step may be performed as needed to obtain a dispersion of toner particles.

[0167] The weight average particle diameter (D4) of the toner particles is preferably 4.0 μm or more and 12.0 μm or less, more preferably 5.0 μm or more and 8.0 μm or less.

[0168] The average circularity of the toner particles is preferably 0.940 or more and 0.995 or less, more preferably 0.950 or more and 0.990 or less, still more preferably 0.970 or more and 0.990 or less.

[0169] The glass transition temperature Tg of the toner particles is preferably 40° C. or higher and 70° C. or lower, and more preferably 50° C. or higher and 60° C. or lower.

[0170] Next, constituent materials of the toner particles will be described.

[0171] Binder resin

[0172] Preferred examples of the binder resin include vinyl resins and polyester resins. Examples of the vinyl resins, polyester resins and other binder resins include the following resins and polymers.

[0173] Homopolymers of styrene and its substituents, such as polystyrene and polyvinyl toluene; styrene copolymers such as styrene-propylene copolymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer and styrene-maleic acid ester copolymer; and polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin and aromatic petroleum resin. These binder resins may be used alone or in combination.

[0174] Examples of polymerizable monomers that can be used to produce vinyl resins include styrene monomers such as styrene and α-methylstyrene; acrylic acid esters such as methyl acrylate and butyl acrylate; methacrylic acid esters such as methyl methacrylate, 2-hydroxyethyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; nitrile vinyl monomers such as acrylonitrile; halogen-containing vinyl monomers such as vinyl chloride; and nitro vinyl monomers such as nitrostyrene.

[0175] In addition to these monomers, the aforementioned 1 The monomers described can also be used here.

[0176] The binder resin preferably contains a carboxyl group, and is preferably a resin produced using a polymerizable monomer containing a carboxyl group.

[0177] Examples of the polymerizable monomer 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.

[0178] Polyester resins obtained by polycondensation of the carboxylic acid components and alcohol components listed below can be used as the 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.

[0179] The polyester resin may be a polyester resin containing a urea group. Preferably, the polyester resin has an uncapped carboxyl group, for example, at a terminal.

[0180] In addition to these monomers, the aforementioned 1 The monomers described can also be used here.

[0181] In order to control the molecular weight of the binder resin, a cross-linking agent may be added during the polymerization of the polymerizable monomer.

[0182] 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-acryloyloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butanediol 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 diacrylate (MANDA, manufactured by Nippon Kayaku Co., Ltd.), and conversion of the above acrylates into methacrylates.

[0183] Preferably, the amount of the cross-linking agent added is 0.001 parts by mass or more and 15.000 parts by mass or less relative to 100 parts by mass of the polymerizable monomer.

[0184] release agent

[0185] The toner particles preferably contain a release agent. The toner particles preferably contain an ester wax having a melting point of 60° C. or higher and 90° C. or lower. Such wax exhibits excellent compatibility with the binder resin and therefore easily produces a plasticizing effect.

[0186] Examples of the ester wax include waxes having fatty acid esters as main components such as carnauba wax and montanic acid ester wax; products of completely or partially deacidified acid components of fatty acid esters such as deacidified carnauba wax; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like; saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; diester products of saturated aliphatic dicarboxylic acids and saturated aliphatic alcohols such as disebenyl sebacate, distearyl dodecanedioate, and distearyl octadecanediol; and diester products of saturated aliphatic diols and saturated aliphatic monocarboxylic acids such as nonanediol dibehenate and dodecanediol distearate.

[0187] Among them, preferably, the wax comprises a difunctional ester wax (diester) having two ester bonds in its molecular structure.

[0188] The difunctional ester wax is an ester compound of a diol and an aliphatic monocarboxylic acid, or an ester compound of a dicarboxylic acid and an aliphatic monoalcohol.

[0189] Specific examples of the aliphatic monocarboxylic acid 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.

[0190] Specific examples of the aliphatic monohydric alcohol include myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, and triacontanol.

[0191] Specific examples of dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0192] Specific examples of the diol 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, spirodiol, 1,4-benzenediol, bisphenol A, and hydrogenated bisphenol A.

[0193] Other examples of release agents that can be used include petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and vaseline; montan wax and derivatives thereof; hydrocarbon waxes obtained by the Fischer-Tropsch process and derivatives thereof; polyolefin waxes and derivatives thereof such as polyethylene and polypropylene; natural waxes and derivatives thereof such as carnauba wax and candelilla wax; and fatty acids such as higher fatty alcohols, stearic acid and palmitic acid.

[0194] The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less relative to 100.0 parts by mass of the binder resin.

[0195] Colorants

[0196] The toner particles may contain a colorant. The colorant is not particularly limited, and known colorants such as those described below may be used.

[0197] Examples of yellow pigments include yellow iron oxide, and condensed azo compounds such as Navel Orange, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, and Lemon Yellow Lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, they are listed below.

[0198] CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168 and 180.

[0199] Examples of red pigments include Indian red, such as Permanent Red 4R, Lithol Red, pyrazolone red, apparent red calcium salt, Lake Red C, Lake Red D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, and other condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, they are listed below.

[0200] 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.

[0201] Examples of blue pigments include copper phthalocyanine compounds and derivatives thereof such as basic blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, and indanthrene blue BG, anthraquinone compounds, and basic dye lake compounds. Specifically, they are listed below.

[0202] CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0203] Examples of black pigments include carbon black and aniline black. These colorants may be used alone or as a mixture thereof, or in a solid solution state.

[0204] The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less relative to 100.0 parts by mass of the binder resin.

[0205] External additives

[0206] For the toner, various organic or inorganic fine powders may be used together as external additives in the toner particles as long as the above characteristics or the above effects are not impaired.

[0207] The measurement methods of various physical properties are described below.

[0208] Method for measuring weight average particle size (D4) and number average particle size (D1) of toner particles

[0209] The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner particles are determined as follows.

[0210] The measuring instrument used was a “Coulter Counter Multisizer 3” (registered trademark, Beckman Coulter, Inc.), a precision particle size distribution measuring instrument operating based on a pore electrical resistance method and equipped with a 100-μm orifice tube.

[0211] The measurement conditions were set and the measurement data were analyzed using the accompanying dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter, Inc.) The number of effective measurement channels was 25,000 channels.

[0212] The electrolyte aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to obtain a concentration of 1.0%, and for example, "ISOTON II" (Beckman Coulter, Inc.) can be used.

[0213] Prior to measurement and analysis, the dedicated software was configured as follows.

[0214] In the "Standard Operating Method Modification (SOMME)" interface of the dedicated software, the total count in control mode was set to 50,000 particles; the number of measurements was set to 1; and the Kd value was set to the value obtained using "Standard Particles 10.0 μm" (Beckman Coulter, Inc.).

[0215] The threshold and noise level were automatically set by pressing the "Threshold / Noise Level Measurement Button." Additionally, the current was set to 1,600 μA, the gain to 2, the electrolyte solution to ISOTON II, and the "Flush the Orifice Tube After Measurement" checkbox was checked.

[0216] In the "Set Pulse to Particle Size Conversion" interface of the dedicated software, the element interval is set to logarithmic particle size; the particle size element is set to 256 particle size elements; and the particle size range is set to 2 μm to 60 μm.

[0217] The specific measurement method is as follows.

[0218] (1) Add 200.0 mL of electrolyte aqueous solution to a 250 mL round-bottom glass beaker dedicated to the Multisizer 3, place it on the sample stage, and stir counterclockwise with a stirring rod at 24 revolutions per second. Contaminants and bubbles in the nozzle are initially removed using the "Nozzle Rinse" function of the dedicated software.

[0219] (2) 30.0 mL of the electrolyte aqueous solution was added to a 100 mL flat-bottom glass beaker. 0.3 mL of a dispersant diluent prepared by diluting "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, containing a nonionic surfactant, an anionic surfactant, and an organic builder, from Wako Pure Chemical Industries, Ltd.) three times (by mass) with deionized water was added thereto.

[0220] (3) Prepare an "Ultrasonic Dispersion System Tetra 150" (Nikkaki Bios Co., Ltd.); this is an ultrasonic disperser equipped with two oscillators (oscillation frequency = 50 kHz), a phase shift of 180°, and an electrical output of 120 W. 3.3 L of deionized water was introduced into the water tank of the ultrasonic disperser, and 2.0 mL of Contaminon N was added to the water tank.

[0221] (4) The beaker described in (2) is placed in the beaker holder opening on the ultrasonic disperser, and the ultrasonic disperser is activated. The height of the beaker is adjusted so that the resonance state of the surface of the aqueous electrolyte solution in the beaker is maximized.

[0222] (5) While the electrolyte aqueous solution in the beaker set according to (4) is being irradiated with ultrasonic waves, 10 mg of the toner particles are added to the electrolyte aqueous solution in small aliquots and dispersed. The ultrasonic dispersion treatment is continued for an additional 60 seconds. The water temperature in the water tank during ultrasonic dispersion can be appropriately controlled to be 10°C or higher and 40°C or lower.

[0223] (6) The electrolyte aqueous solution containing the dispersed toner particles prepared in (5) is dripped into the round-bottom beaker set on the sample stage as described in (1) using a pipette and adjusted to obtain a measurement concentration of 5%. Measurement is then performed until the number of particles measured reaches 50,000.

[0224] (7) Analyze the measurement data using the dedicated software included with the instrument to calculate the weight-average particle size (D4) and number-average particle size (D1). When the dedicated software is set to Graph / Volume %, the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4). When the dedicated software is set to Graph / Number %, the "Average Particle Size" on the "Analysis / Number Statistics (Arithmetic Mean)" screen is the number-average particle size (D1).

[0225] Measurement method of glass transition temperature (Tg)

[0226] The glass transition temperature (Tg) of, for example, a binder resin, a toner, and the like is measured using a differential scanning calorimeter (hereinafter also referred to as “DSC”).

[0227] The measurement of the glass transition temperature is performed by DSC in accordance with JIS K 7121 (International Standard: ASTM D 3418-82).

[0228] "Q1000" (TA Instruments) was used for the measurement, and the temperature of the instrument detection portion was calibrated using the melting points of indium and zinc, and the heat of fusion of indium was used for the calibration.

[0229] During measurement, 10 mg of a measurement sample was precisely weighed and placed in an aluminum pan; an empty aluminum pan was used as a control.

[0230] In the first temperature increase process, measurement is performed while heating the measurement sample from 20° C. to 200° C. at 10° C. / min. Then, it is maintained at 200° C. for 10 minutes and then cooled from 200° C. to 20° C. at 10° C. / min.

[0231] Then, after being maintained at 20°C for 10 minutes, the temperature was increased again from 20°C to 200°C at a rate of 10°C / min in the second heating process.

[0232] The glass transition temperature here is the midpoint glass transition temperature. Using the DSC curve from the second temperature increase process obtained under the above-mentioned measurement conditions, the glass transition temperature (Tg) is taken as the temperature at the intersection of the curve portion where the glass transition temperature changes stepwise and a straight line equidistant in the longitudinal direction from the extended straight line of each base line on the low temperature side and the high temperature side of the stepwise change.

[0233] When toner particles are produced in, for example, an aqueous medium, a portion is taken as a sample, and DSC measurement is performed on it after washing away substances other than the toner particles and drying.

[0234] Measurement method of average circularity

[0235] The toner and the average circularity of toner particles are measured using "FPIA-3000" (Sysmex Corporation), a flow particle image analyzer, under the measurement and analysis conditions during the calibration work.

[0236] The specific measurement process is as follows.

[0237] First, 20 mL of deionized water (e.g., from which solid impurities have been removed in advance) is introduced into a glass container. To this is added approximately 0.2 mL of a dispersant diluent prepared by diluting "Contaminon N" (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, containing a nonionic surfactant, an anionic surfactant, and an organic builder, from Wako Pure Chemical Industries, Ltd.) three times (by mass) with deionized water.

[0238] 0.02 g of the measurement sample was added and dispersed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. Cooling was appropriately performed during this process so that the temperature of the dispersion liquid was 10° C. or higher and 40° C. or lower.

[0239] Using a tabletop ultrasonic cleaner / disperser (e.g., “VS-150” (Velvo-Clear Co., Ltd.)) having an oscillation frequency of 50 kHz and an electrical output of 150 W as an ultrasonic disperser, a predetermined amount of deionized water was introduced into a water tank, and approximately 2 mL of Contaminon N was added to the water tank.

[0240] A flow particle image analyzer equipped with a "UPlanApro" objective lens (10X, numerical aperture: 0.40) was used for the measurement, and a "PSE-900A" (Sysmex Corporation) particle sheath was used for the sheath fluid.

[0241] The dispersion liquid prepared according to the above method is introduced into a flow particle image analyzer, and 3,000 toner particles are measured according to the total count mode in the HPF measurement mode.

[0242] The average circularity of the toner or toner particles is determined while setting the binarization threshold to 85% during particle analysis and limiting the analyzed particle diameter to a circle-equivalent diameter of 1.985 μm or more and less than 39.69 μm.

[0243] For this measurement, automatic focus adjustment is performed before the start of measurement using reference latex particles (e.g., diluted with deionized water from "RESEARCH AND TESTPARTICLES Latex Microsphere Suspensions 5200A", Duke Scientific Corporation). Thereafter, focus adjustment is performed every two hours from the start of measurement.

[0244] Method for measuring the number average particle size of primary particles of polyacid metal salt fine particles

[0245] The number average particle size of the primary particles of the polyacid metal salt fine particles is measured using a scanning electron microscope "S-4800" (trade name, manufactured by Hitachi, Ltd.). The toner having the polyacid metal salt fine particles added thereto is observed, and the major diameters of the primary particles of 100 random external additives are measured in a field of view magnified up to 50,000 times. The observation magnification is appropriately adjusted according to the size of the polyacid metal salt fine particles.

[0246] Method for measuring the normalized intensity of silicon ions present on the surface of toner particles

[0247] The normalized intensity of silicon ions on the toner particle surface was determined using a time-of-flight secondary ion mass spectrometer (TOF-SIMS). The device and measurement conditions used were as follows.

[0248] The measurement is performed in a toner from which external additives such as polyacid metal salt fine particles are removed according to the method described below.

[0249] -Measurement device: nanoTOF II (product name, Ulvac-Phi, Inc.)

[0250] -Main ion species: Bi 3++

[0251] -Accelerating voltage: 30kV

[0252] -Primary ion current: 0.05pA

[0253] -Repetition frequency: 8.2kHz

[0254] - Raster mode: unbunch

[0255] -Grating size: 100μm×100μm

[0256] -Measurement mode: Positive

[0257] -Neutralize electron gun: Use

[0258] - Measurement time: 600 seconds

[0259] -Sample preparation: Toner particles fixed to indium sheets

[0260] -Sample pretreatment: None

[0261] Evaluation was performed based on the mass numbers of Si ions and fragment ions derived from the resin or silane compound using ULVAC-PHI standard software (TOF-DR).

[0262] The normalized intensity of silicon ions (m / z 28) can be obtained by dividing the intensity of ions derived from silicon (m / z 28) with a mass number of 28 by the total intensity of ions with mass numbers from 1 to 1850.

[0263] The fact that the normalized intensity of silicon ions (m / z 28) originates from the condensation products of organosilicon compounds is explained in this paper by the following 29 Si-NMR (solid) measurement was confirmed. In the case where the toner particles contain a silicon compound other than the condensation product of the organic silicon compound, the content ratio of the condensation product of the organic silicon compound to the silicon compound contained in the toner particles is based on 29 The value obtained by multiplying the normalized intensity of silicon ions (m / z 28) by their content ratio was determined by Si-NMR (solid) measurement.

[0264] Method for measuring the normalized intensity of silicon ions present inside toner particles

[0265] Generally, TOF-SIMS is a surface analysis method that produces data in the depth direction of about 1 nm. Therefore, after the toner is sputtered by an argon gas cluster ion beam (Ar-GCIB) and the surface is scraped, the intensity inside the toner is determined.

[0266] After sputtering the toner particles under the following conditions, the normalized intensity of silicon ions (m / z 28) measured according to the same conditions as in the above “Method of measuring the normalized intensity of silicon ions present on the surface of toner particles” is taken as the value of the normalized intensity of silicon ions present inside the toner particles.

[0267] The sputtering conditions were as follows.

[0268] Accelerating voltage: 5 kV

[0269] Current: 6.5nA

[0270] Grating size: 600×600μm

[0271] Irradiation time: 5 sec / cycle

[0272] Splash time: 250 seconds

[0273] Here, a PMMA film was sputtered in advance under the same conditions, and the cutting depth was checked; it was found that a depth of 80 nm was cut within 250 s.

[0274] Removal of polyacid metal salt fine particles and external additives

[0275] Here, 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) was added to 100 mL of ion-exchanged water and dissolved therein while being heated in a hot water bath to prepare a sucrose concentrate. Then, 31 g of this sucrose concentrate and 6 mL of Contaminon N (a 10% aqueous solution of a neutral detergent with a pH of 7 for cleaning precision measuring instruments, containing a nonionic surfactant, anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) were introduced into a centrifuge tube to prepare a dispersion. Then, 1 g of toner was added to this dispersion and toner lumps were broken up using a spatula or the like.

[0276] The centrifuge tube was shaken in a shaker ("KM Shaker" manufactured by Iwaki Industry Co., Ltd.) at a frequency of 350 reciprocating times per minute for 30 minutes. After shaking, the resulting solution was transferred to a glass tube (50 mL) in a swing rotor and centrifuged at 58.33 s using a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.). -1 In the glass tube after centrifugation, toner particles are present in the uppermost layer, and external additives such as polyacid metal salt fine particles are present on the aqueous solution side of the lower layer.

[0277] The toner particles of the uppermost layer were collected, filtered, and washed with 2 L of ion-exchanged water heated to 40° C., and the washed toner particles were recovered.

[0278] Method for measuring number average molecular weight (Mn) and weight average molecular weight (Mw)

[0279] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer, resin, and toner particles are measured by gel permeation chromatography (GPC) as follows.

[0280] First, the sample to be tested was dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution was then filtered through a solvent-resistant membrane filter "MYSYORI DISC" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution was adjusted so that the concentration of the component soluble in THF was approximately 0.8% by mass. The sample solution was then used for measurement under the following conditions.

[0281] Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)

[0282] Chromatographic column: 7-column Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)

[0283] Eluent: tetrahydrofuran (THF)

[0284] Flow rate: 1.0 mL / min

[0285] Oven temperature: 40.0℃

[0286] Sample injection volume: 0.10mL

[0287] To calculate the molecular weight of the sample, a molecular weight calibration curve generated 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, manufactured by Tosoh Corporation) was used.

[0288] Method for extracting silane-modified resin R from toner particles

[0289] The silane-modified resin R in the toner particles is recovered by separating the extracted product in tetrahydrofuran (THF) according to a solvent gradient elution method. The preparation method is as follows.

[0290] Here, 10.0 g of toner particles were weighed, placed on cylindrical filter paper (No. 84, manufactured by Toyo Roshi Kaisha, Ltd.), and placed in a Soxhlet extractor. Extraction was performed for 20 hours using 200 mL of THF as a solvent, and the solvent was removed from the resulting extract to obtain a solid, which was a THF-soluble substance. This THF-soluble substance contained the silane-modified resin R. This operation was repeated multiple times to obtain the desired amount of THF-soluble substance.

[0291] Gradient preparative HPLC (LC-20AP high pressure gradient preparative system manufactured by Shimadzu Corporation, SunFire preparative column manufactured by Waters Co., Ltd.) The column was eluted with a column diameter of 250 mm (1 / 4 in). The column temperature was 30°C, the flow rate was 50 mL / min, acetonitrile was used as the poor solvent for the mobile phase, and THF was used as the good solvent. A solution of 0.02 g of the THF-soluble material obtained by extraction in 1.5 mL of THF was used as the sample for separation.

[0292] The mobile phase starts with a composition of 100% acetonitrile. After 5 minutes of sample injection, the proportion of THF is increased by 4% per minute until the mobile phase composition is 100% THF after 25 minutes. The components can be separated by drying the obtained fractions. As a result, resin R can be obtained. The fraction composition of resin R can be determined by measuring the content of silicon atoms as described below and 13 C-NMR measurement.

[0293] Confirmation of the structure of condensation products of organosilicon compounds

[0294] pass 1 H-NMR analysis, 13 C-NMR analysis, 29 Si-NMR analysis and FT-IR analysis were used to confirm the functional groups contained in the condensation product of the organic silicon compound and the polymer site P in the structure represented by formula (1). 1 and L 1 Part and R 1 to R 3 The structure of the part.

[0295] When the condensation product of the organosilicon compound is a silane-modified resin R, the measurement sample used is the synthesized silane-modified resin R or the silane-modified resin R extracted from the toner particles by the above-mentioned extraction method. When the condensation product of the organosilicon compound is a condensation product of a silane coupling agent, THF-insoluble matter of the toner particles is used.

[0296] In the structure represented by formula (1), R 1 to R 3 In the case where the silicon atom is bonded to an alkoxy group or a hydroxyl group, the following " 29 The valence of the alkoxy group or the hydroxyl group relative to the silicon atom was determined by the method shown in "Si-NMR (Solid) Measurement Conditions".

[0297] 29 Si-NMR (solid) measurement conditions

[0298] Equipment: JEOL RESONANCE Co., Ltd.'s JNM-ECX500II

[0299] Sample tube:

[0300] Sample size: 150 mg

[0301] Measuring temperature: room temperature

[0302] Pulse mode: CP / MAS

[0303] Measured core frequency: 97.38MHz ( 29 Si)

[0304] Reference substance: DSS (external standard: 1.534ppm)

[0305] Sample speed: 10kHz

[0306] Contact time: 10ms

[0307] Delay time: 2 seconds

[0308] Scan times: 2000 to 8000 times

[0309] As a result of the above measurement, the abundance ratio can be calculated by curve fitting of multiple silane components based on the number of oxygen atoms bonded to Si and by peak separation / integration. In this way, the R of the resin represented by formula (1) can be confirmed. 1 to R 3 The valence of the alkoxy group or hydroxyl group relative to the silicon atom.

[0310] Compounds having at least one of the following M unit, D unit, or T unit structures can be considered as condensation products of organosilicon compounds. Compounds having the following Q unit structure can be considered as silicon compounds other than condensation products of organosilicon compounds.

[0311] In the following structures, at least one R in each unit is a carbon atom. The other R is any group; for example, similar to R in formula (1): 1 to R 3 , other R represents a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxyl group.

[0312]

[0313] P in the silane-modified resin R represented by formula (1) 1 、L 1 and R 1 to R 3 The structure can be based on13 The results were confirmed by C-NMR (solid state) measurement. The measurement conditions were as follows.

[0314] 13 C-NMR (solid) measurement conditions

[0315] Equipment: JEOL RESONANCE Co., Ltd.'s JNM-ECX500II

[0316] Sample tube:

[0317] Sample size: 150 mg

[0318] Measuring temperature: room temperature

[0319] Pulse mode: CP / MAS

[0320] Measured core frequency: 123.25MHz ( 13 C)

[0321] Reference substance: Adamantane (external standard: 29.5ppm)

[0322] Sample speed: 20kHz

[0323] Contact time: 2ms

[0324] Delay time: 2s

[0325] Scan times: 1024 times

[0326] According to P in formula (1) 1 、L 1 and R 1 to R 3 The type of peaks is separated and the peaks are identified to determine the P 1 、L 1 and R 1 to R 3 type.

[0327] Measurement of polymerization conversion rate of polymerizable monomers

[0328] The polymerization conversion rate of the polymerizable monomer can be measured by gas chromatography (GC) as follows.

[0329] Here, 2.55 mg of DMF (dimethylformamide) was added to 100 ml of acetone to prepare a solvent containing an internal standard. Next, 0.2 g of the polymerizable monomer composition dispersion was accurately weighed, and 10 ml of the solution was prepared using the above solvent. The solution was vibrated in an ultrasonic oscillator for 30 minutes and then allowed to stand for 1 hour. The solution was then filtered through a 0.5 μm membrane filter, and 4 μl of the resulting filtrate was analyzed by gas chromatography.

[0330] A calibration curve was prepared in advance, and the mass ratio / area ratio of the polymerizable monomer to the internal standard DMF was calculated. The amount of unreacted polymerizable monomer was calculated from the obtained spectrum to determine the polymerization conversion rate.

[0331] The measuring device and measuring conditions are as follows.

[0332] GC: GC-14A from Shimadzu Corporation

[0333] Column: J&W Scientific, Inc., DB-WAX (249μm×0.25μm×30m)

[0334] Carrier gas: N2

[0335] Oven: (1) Keep at 70°C for 2 minutes; (2) Heat at 5°C / min to 220°C

[0336] Inlet: 200℃

[0337] Split ratio: 1:20

[0338] Detector: 200℃ (FID)

[0339] Measurement of the total content of Ca and Mg elements in toner particles

[0340] The total content of Ca and Mg elements derived from the dispersant and the like was quantified using an inductively coupled plasma atomic emission spectrometer (ICP-AES (manufactured by Seiko Instruments Inc.)).

[0341] As a pretreatment, acid decomposition was performed in 100.0 mg of the toner particles using 8.00 ml of 60% nitric acid (manufactured by Kanto Chemical Co., Inc.; for atomic absorption spectrometry).

[0342] The acid decomposition involves treating at an internal temperature of 220° C. for 1 hour in a sealed container using a microwave high-power sample pretreatment device ETHOS 1600 (manufactured by Milestone Srl) to prepare a solution sample containing a polyvalent metal element.

[0343] Ultrapure water was then added to a total of 50.00 g to produce a measurement sample. A calibration curve was created for each polyvalent metal element, and the amount of metal contained in each sample was quantified. Separately, ultrapure water was added to 8.00 ml of nitric acid to a total of 50.00 g, and the resulting solution was measured as a blank; the metal amount in the blank was then subtracted.

[0344] Example

[0345] The present invention will be further described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specifically stated, "parts" refer to parts by mass in all cases.

[0346] Production Example of Resin R1

[0347] The following materials were charged into an autoclave equipped with a decompression device, a water separation device, a nitrogen introduction device, a temperature measuring device and a stirring device, and reacted at 200°C under normal pressure and a nitrogen atmosphere for 20 hours.

[0348] - Alcohol component: 80.9 parts

[0349] (2.0 mol adduct of bisphenol A-propylene oxide)

[0350] - Acid component 1 (terephthalic acid): 16.1 parts

[0351] - Acid component 2 (isophthalic acid): 16.1 parts

[0352] -Tetrabutoxy titanate: 0.2 parts

[0353] Then, the following materials were added, and the reaction was allowed to proceed at 220° C. for 3 hours.

[0354] - Acid or alcohol component 3 (trimellitic acid): 0.4 parts

[0355] -Tetrabutoxy titanate: 0.3 parts

[0356] The reaction was further carried out under reduced pressure within the range of 10 to 20 mmHg for 2 hours.The obtained resin was dissolved in chloroform, and the obtained solution was added dropwise to ethanol, followed by precipitation and filtration, thereby obtaining a polyester resin.

[0357] The carboxyl groups in the obtained polyester resin and the amino groups in the aminosilane were amidated as follows to produce resin R1.

[0358] Here, 100.0 parts of the above polyester was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added, and stirred at room temperature for 5 hours. Once the reaction was complete, the solution was added dropwise to methanol, and then precipitated and filtered to obtain resin R1.

[0359] -Silane compound (3-aminopropyltrimethoxysilane): 0.2 parts

[0360] -Triethylamine: 0.3 parts

[0361] -Condensation agent (amidating agent): 0.3 parts

[0362] [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride]

[0363] Table 1 shows the structure and physical properties of the obtained resin R1.

[0364] Production Example of Resin R2

[0365] The following materials were charged into an autoclave equipped with a decompression device, a water separation device, a nitrogen introduction device, a temperature measuring device and a stirring device, and reacted at 200° C. under normal pressure and a nitrogen atmosphere for 5 hours.

[0366] - Alcohol component: 93.2 parts

[0367] (2.0 mol adduct of bisphenol A-propylene oxide)

[0368] - Acid component 1 (terephthalic acid): 11.2 parts

[0369] - Acid component 2 (isophthalic acid): 11.2 parts

[0370] -Tetrabutoxy titanate: 0.2 parts

[0371] Then, the following materials were added, and the reaction was allowed to proceed at 220° C. for 3 hours.

[0372] -Tetrabutoxy titanate: 0.3 parts

[0373] The reaction pressure, reaction temperature and reaction time are appropriately adjusted to obtain products with lower molecular weight.

[0374] The carboxyl groups in the obtained polyester and the amino groups in the aminosilane were amidated as follows to produce resin R2.

[0375] Here, 100 parts of the above polyester was dissolved in 400 parts of N,N-dimethylacetamide, and the following materials were added. The mixture was stirred at room temperature for 5 hours. Once the reaction was complete, the resulting solution was added dropwise to methanol, followed by precipitation and filtration to obtain resin R2.

[0376] -Silane compound (3-aminopropylmethyldimethoxysilane): 1.2 parts

[0377] -Triethylamine: 2.4 parts

[0378] -Condensation agent (amidating agent): 2.4 parts

[0379] [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine hydrochloride]

[0380] Table 1 shows the structure and physical properties of the obtained resin R2.

[0381] Production Examples of Resins R3 to R5 and Resin R7

[0382] Resins R3 to R5 and Resin R7 were obtained in the same manner as in the Production Example of Resin R2, except that the silane compound, triethylamine, and condensing agent were changed as shown in Table 1.

[0383] Table 1 shows the structure and physical properties of the obtained resin.

[0384] Production Example of Resin R6

[0385] Here, 100.0 parts of propylene glycol monomethyl ether was heated while purging with nitrogen and refluxed at a liquid temperature of 120° C. or higher. Then, a mixture of the following materials was added dropwise over 3 hours.

[0386] -Styrene: 64.1 parts

[0387] -Butyl acrylate: 30.9 parts

[0388] - Acrylic acid: 5.0 parts

[0389] - tert-Butyl peroxybenzoate: 1.0 part

[0390] (Organic peroxide-based polymerization initiator, manufactured by NOF Corporation, trade name: Perbutyl Z)

[0391] Upon completion of the dropwise addition, the solution was stirred for 3 hours and then distilled under normal pressure while raising the liquid temperature to 170°C. Once the liquid temperature reached 170°C, the pressure was reduced to 1 hPa and the solvent was removed by distillation for 1 hour to obtain a solid resin product. The solid resin product was dissolved in tetrahydrofuran and reprecipitated with n-hexane; the precipitated solid was then filtered to obtain a styrene acrylic resin.

[0392] The carboxyl groups in the obtained styrene acrylic resin and the amino groups in the aminosilane were amidated as follows to produce resin R6.

[0393] Here, 100 parts of the above-mentioned styrene acrylic copolymer was dissolved in 400 parts of N,N-dimethylacetamide, and the following materials were added. The mixture was stirred at room temperature for 5 hours. Once the reaction was complete, the solution was added dropwise to methanol, followed by precipitation and filtration to obtain Resin R6.

[0394] -Silane compound (3-aminopropyltrimethylsilane): 1.0 part

[0395] -Triethylamine: 2.7 parts

[0396] -Condensation agent: 2.7 parts

[0397] [DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholine hydrochloride]

[0398] Table 1 shows the structure and physical properties of the obtained resin R6.

[0399] [Table 1]

[0400]

[0401] In the table, P1, L1, and R1 to R3 correspond to P in formula (1). 1 、L 1 and R 1 to R 3 In the table, R5 corresponds to R in formula (2) 5 , and represents a propyl group. In addition, Me represents a methyl group, and Et represents an ethyl group.

[0402] The abbreviations in the table are as follows.

[0403] BPA(PO): 2.0 mole adduct of bisphenol A-propylene oxide

[0404] TPA: terephthalic acid

[0405] IPA: Isophthalic acid

[0406] St:Styrene

[0407] BA: Butyl acrylate

[0408] AA: Acrylic acid

[0409] Production Example of Toner Particles 1

[0410] Preparation of polymerizable monomer composition 1

[0411] - 60.0 parts of styrene

[0412] -CI Pigment Blue 15:3 6.3 parts

[0413] The above materials were charged into an attritor (Nippon Coke & Engineering Co., Ltd.) and dispersed at 220 rpm for 5.0 hours using zirconium oxide particles having a diameter of 1.7 mm, and then the zirconium oxide particles were removed to obtain a colorant dispersion in which a pigment was dispersed.

[0414] Then, the following materials were added to the above colorant dispersion.

[0415]

[0416] (Polycondensation product of terephthalic acid and 2 mol of propylene oxide adduct of bisphenol A; weight average molecular weight Mw is 10,000; acid value is 8.2 mgKOH / g)

[0417] - Release agent (hydrocarbon wax; melting point: 79°C) 5.0 parts

[0418] -Plasticizer (ethylene glycol distearate) 15.0 parts

[0419] As a dissolution / dispersion process, the above materials were subsequently kept at 65° C. and uniformly dissolved and dispersed using a TK homomixer at 500 rpm, thereby preparing a polymerizable monomer composition.

[0420] Preparation of aqueous medium 1

[0421] Here, 11.2 parts of sodium phosphate (dodecahydrate) are added to the reaction vessel containing 390.0 parts of ion exchange waters, and when purged with nitrogen, the whole is incubated at 65 ℃ for 1.0 hour. Use TK homomixer (TokushuKika Kogyo Co., Ltd. system) to stir with 12000rpm. While keeping stirring, 7.4 parts of calcium chloride (dihydrate) are dissolved in 10.0 parts of ion exchange waters and the calcium chloride aqueous solution obtained is disposable dropped in the reaction vessel, thereby prepare the aqueous medium comprising dispersion stabilizer. Then, 1.0mol / L hydrochloric acid is added to the aqueous medium in the reaction vessel, so that pH is adjusted to 6.0, thereby prepare aqueous medium 1.

[0422] Granulation step

[0423] While the temperature of the aqueous medium 1 was maintained at 70°C and the rotation speed of the stirring device was 12,500 rpm, the polymerizable monomer composition was added to the aqueous medium 1 to which 8.0 parts of t-butyl peroxypivalate was added as a polymerization initiator. Granulation was performed for 10 minutes while the stirring device was maintained at 12,500 rpm.

[0424] Polymerization step A

[0425] The high-speed stirring device was converted into a stirrer equipped with a propeller-type stirring blade, and polymerization was carried out for 5.0 hours while stirring at 200 rpm while maintaining the temperature at 70°C.

[0426] Polymerization step B

[0427] After the polymerization step A, the polymerization reaction was carried out by further raising the temperature to 85° C. and heating for 2.0 hours. Then, 0.03 parts of 3-methacryloxypropyltrimethoxysilane (M1) was added and stirred for 5 minutes, and then a 1 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 9.0.

[0428] Residual monomers were removed by heating the mixture to 98°C for 3 hours. The temperature was then lowered to 55°C and maintained at that temperature for 5 hours while stirring. The temperature was then lowered to 25°C. Ion-exchanged water was added to adjust the toner particle concentration in the dispersion to 30.0%, yielding Toner Particle Dispersion Liquid 1 in which Toner Particles 1 were dispersed.

[0429] Washing steps

[0430] The pH of the toner particle dispersion 1 was adjusted to 1.5 using 1 mol / L hydrochloric acid, stirred for 1.0 hour, and then filtered and dried while washing with ion-exchanged water to obtain toner particles 1 .

[0431] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 1 are shown in Table 3.

[0432] Production Example of Toner Particles 2

[0433] Then, Toner Particles 2 were obtained in the same manner as in the Production Example of Toner Particles 1, except that the amount of 3-methacryloxypropyltrimethoxysilane (M1) added in the Production Example of Toner Particles 1 was changed to 0.01 parts.

[0434] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 2 are shown in Table 3.

[0435] Production Example of Toner Particles 3

[0436] A mixed solution of 15.0 parts of ion-exchanged water whose pH had been adjusted to 4.0 by adding 1 mol / L hydrochloric acid and 0.15 parts of 3-methacryloxypropyltrimethoxysilane (M1) was mixed with a stirrer until a uniform phase was formed to obtain a monomer hydrolyzed solution 1.

[0437] Then, toner particles 3 were obtained in the same manner as in the production example of toner particles 1, except that once the polymerization step A in the production example of toner particles 1 was completed, the entire amount of the monomer hydrolyzed liquid 1 was added and stirred for 5 minutes, and then the pH was adjusted to 9.0 by adding a 1 mol / L sodium hydroxide aqueous solution, and except that 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B.

[0438] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 3 are shown in Table 3.

[0439] Production Example of Toner Particles 4

[0440] Then, toner particles 4 were obtained in the same manner as in the production example of toner particles 1, except that here, upon completion of the polymerization step A in the production example of toner particles 1, 0.15 parts of 3-methacryloxypropyltrimethoxysilane (M1) was added and stirred for 5 minutes, and then the pH was adjusted to 9.0 by adding a 1 mol / L sodium hydroxide aqueous solution, and except that 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B.

[0441] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 4 are shown in Table 3.

[0442] Production Example of Toner Particles 5

[0443] A mixed solution of 0.03 parts of ion-exchanged water, the pH of which had been adjusted to 4.0 by adding 1 mol / L hydrochloric acid, and 0.02 parts of methyltrimethoxysilane (M7) was mixed using a stirrer until a uniform phase was formed, thereby obtaining a monomer hydrolyzed solution 2.

[0444] Then, toner particles 5 were obtained in the same manner as in the production example of toner particles 2 except that the entire amount of the monomer hydrolyzed liquid 2 was added immediately after the temperature was lowered to 55° C. in the production example of toner particles 2.

[0445] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 5 are shown in Table 3.

[0446] Production Example of Toner Particles 6

[0447] Then, toner particles 6 were obtained in the same manner as in the production example of toner particles 1, except that 0.01 parts of 3-methacryloxypropyltrimethoxysilane (M1) in the production example of toner particles 1 was changed to 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).

[0448] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 6 are shown in Table 3.

[0449] Production Example of Toner Particles 7

[0450] Then, toner particles 7 were obtained in the same manner as in the production example of toner particles 6, except that the stirring time until the pH was adjusted to 9.0 was changed to 60 minutes after adding 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) in the production example of toner particles 6.

[0451] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 7 are shown in Table 3.

[0452] Production Example of Toner Particles 8

[0453] Then, toner particles 8 were obtained in the same manner as in the production example of toner particles 6, except that the addition of 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) in the production example of toner particles 6 was changed to after the temperature in the polymerization step B was lowered to 55°C, and except that the addition was followed by stirring for 60 minutes, followed by addition of a 1 mol / L aqueous sodium hydroxide solution to adjust the pH to 9.0, and thereafter the temperature was maintained at 55°C for 4.0 hours while maintaining stirring.

[0454] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 8 are shown in Table 3.

[0455] Production Examples of Toner Particles 9 to 12

[0456] Toner Particles 9 to 12 were obtained in the same manner as in the Production Example of Toner Particles 1, except that 3-methacryloxypropyltrimethoxysilane (M1) in the Production Example of Toner Particles 1 was changed as given in Table 3.

[0457] The silane compounds used are shown in Table 2, and the physical properties of the obtained toner particles 9 to 12 are shown in Table 3.

[0458] Production Example of Toner Particles 13

[0459] Preparation of aqueous medium 2

[0460] Here, 10.2 parts of magnesium chloride are added to the reaction vessel containing 250.0 parts of ion exchange waters, and when purging with nitrogen, the whole is incubated at 65 DEG C for 1.0 hour. Use TK homomixer (Tokushu Kika Kogyo Co., Ltd. system) to stir with 12000rpm. While keeping stirring, the calcium chloride aqueous solution obtained by dissolving 6.2 parts of calcium chloride in 50.0 parts of ion exchange waters is once added to the reaction vessel, to prepare the aqueous medium comprising dispersion stabilizer. Then, 1.0mol / L hydrochloric acid is added to the aqueous medium in the reaction vessel, so that the pH is adjusted to 6.0, thereby preparing aqueous medium 2.

[0461] Then, toner particles 13 were obtained in the same manner as in the production example of toner particles 1 except that the aqueous medium 1 in the production example of toner particles 1 was changed to the aqueous medium 2 here.

[0462] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 13 are shown in Table 3.

[0463] Production Example of Toner Particles 14

[0464] Toner Particles 14 were obtained in the same manner as in the Production Example of Toner Particles 13, except that the amount of magnesium chloride was changed to 12.2 parts. Table 3 shows the physical properties of the obtained Toner Particles 14.

[0465] Production Example of Toner Particles 15

[0466] Then, Toner Particles 15 were obtained in the same manner as in the Production Example of Toner Particles 1, except that 5.0 parts of the polyester resin in the Production Example of Toner Particles 1 was changed to 4.5 parts of the polyester resin and 1.00 part of the resin R1. Table 3 shows the physical properties of the obtained Toner Particles 15.

[0467] Production Examples of Toner Particles 16 to 21 and 25

[0468] Toner particles 16 to 21 and 25 were obtained in the same manner as in the production example of toner particle 15, except that resin R1 in the production example of toner particle 15 was changed to any one of resins R2 to R7 in the amount given in Table 3. Table 3 shows the physical properties of the obtained toner particles 16 to 21 and 25.

[0469] Production Example of Toner Particles 22

[0470] Preparation of binder resin particle dispersion

[0471] Here, 89.5 parts of styrene, 9.2 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution obtained by dissolving 1.5 parts of Neogen RK (manufactured by DKS Co., Ltd.) in 150 parts of ion-exchanged water was dispersed and added to the above solution.

[0472] While slowly stirring for 10 minutes, an aqueous solution prepared by dissolving 0.3 parts of potassium persulfate in 10 parts of ion-exchanged water was further added. After nitrogen substitution, 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 having a solids concentration of 12.5% by mass and a volume-based median particle size of 0.2 μm.

[0473] The binder resin constituting the resin particles has a carboxyl group derived from acrylic acid and has a glass transition temperature of 57°C.

[0474] Preparation of wax dispersion

[0475] Here, 100 parts of a diester compound (ethylene glycol distearate), 30 parts of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd.; melting point 75°C) as a mold release wax, and 20 parts of Neogen RK were mixed with 400 parts of ion-exchanged water. The resulting mixture was then dispersed for about 1 hour using a wet jet mill JN100 (manufactured by Jokoh Co., Ltd.) to obtain a wax dispersion.

[0476] Preparation of colorant dispersion

[0477] Here, CI Pigment Blue 15:3 (100 parts) and 15 parts of Neogen RK as a colorant were mixed with 885 parts of ion-exchanged water, and the resultant mixture was dispersed for about 1 hour using a wet jet mill JN 100 to obtain a colorant dispersion.

[0478] Then, 265 parts of the obtained binder resin particle dispersion, 80 parts of the wax dispersion, and 10 parts of the colorant dispersion were dispersed using a homogenizer (Ultra-Turrax T50, manufactured by IKA KK). While stirring, the temperature in the container was adjusted to 30° C., and the pH was adjusted to 8.0 by adding a 1 mol / L sodium hydroxide aqueous solution.

[0479] While stirring at 30°C, an aqueous solution obtained by dissolving 0.5 parts of magnesium chloride in 10 parts of ion-exchanged water was added as a flocculant over 10 minutes. After standing for 3 minutes, the temperature was raised to 50°C to generate aggregated particles. In this state, the particle size of the aggregated particles was measured using a "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Inc.). When the weight-average particle size reached 6.5 μm, 3.0 parts of sodium chloride and 8.0 parts of Neogen RK were added to stop particle growth.

[0480] The pellets were then heated to 95°C and stirred in this state to effect melt adhesion and spheroidization of the aggregated particles. When the average circularity reached 0.980, the pellets were cooled to 80°C and maintained at 80°C. Ice water was then added to cool the pellets at a cooling rate of 3°C / sec from the cooling start temperature of 80°C to the cooling end temperature of 30°C.

[0481] Then, while adding 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) and stirring for 60 minutes, the temperature was raised to 55° C. again. Thereafter, the pH was adjusted to 9.0 by adding a 1 mol / L sodium hydroxide aqueous solution, and the temperature was maintained at 55° C. for 4.0 hours while stirring, followed by cooling to 25° C. to obtain a toner particle dispersion 22.

[0482] The pH of the obtained toner particle dispersion 22 was adjusted to 1.5 using 1 mol / L hydrochloric acid, stirred for 1.0 hour, and then, filtered while washing with ion-exchanged water, and dried, thereby obtaining toner particles 22 .

[0483] The silane compounds used are shown in Table 2, and the physical properties of the obtained toner particles 22 are shown in Table 3.

[0484] Production Example of Toner Particles 23

[0485] -Binder resin (styrene-n-butyl acrylate copolymer): 100.0 parts

[0486] [The styrene-n-butyl acrylate copolymerization ratio (mass ratio) is 75:25, the peak molecular weight (Mp) is 22,000, the weight average molecular weight (Mw) is 35,000, and Mw / Mn = 2.4, where Mn represents the number average molecular weight.]

[0487] -CI Pigment Blue 15:3 6.3 parts

[0488] - Release agent (hydrocarbon wax; melting point 79°C) 5.0 parts

[0489] -Plasticizer (ethylene glycol distearate) 5.0 parts

[0490] The above materials were pre-mixed using an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) and then melt-kneaded using a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Corp.) to obtain a kneaded product. The obtained kneaded product was cooled, coarsely pulverized using a hammer mill (manufactured by Hosokawa Micron Corporation), and then pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.) to obtain a finely pulverized powder.

[0491] The obtained finely pulverized powder was re-slurried in aqueous medium 1 to produce a dispersion again, after which the temperature was raised to 55°C again. 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2) was then added, followed by stirring for 60 minutes. The pH was then adjusted to 9.0 by adding a 1 mol / L aqueous sodium hydroxide solution, and the mixture was maintained at 55°C for 4.0 hours while stirring, and then cooled to 25°C to obtain a toner particle dispersion 23.

[0492] The pH of the obtained toner particle dispersion 23 was adjusted to 1.5 using 1 mol / L hydrochloric acid, stirred for 1.0 hour, and then filtered and dried while washing with ion-exchanged water to obtain toner particles 23 .

[0493] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 23 are shown in Table 3.

[0494] Production Example of Toner Particles 24

[0495] Toner particles 24 were obtained in the same manner as in the production example of toner particles 3 except that 3-methacryloxypropyltrimethoxysilane (M1) in the production example of toner particles 3 was changed to 0.50 parts.

[0496] The silane compounds used are shown in Table 2, and the physical properties of the obtained toner particles 24 are shown in Table 3.

[0497] Production Example of Toner Particles 26

[0498] Toner particles 26 were obtained in the same manner as in the production example of toner particles 1, except that 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B of the production example of toner particles 1.

[0499] The physical properties of the obtained toner particles 26 are given in Table 3. The normalized intensity of the toner particles 26 in Table 3 is a value derived from a base intensity (base).

[0500] Production Example of Toner Particles 27

[0501] Then, toner particles 27 were obtained in the same manner as in the production example of toner particles 24 except that 3-methacryloxypropyltrimethoxysilane (M1) was changed to 0.40 parts of 3-methacryloxypropyltris(trimethylsiloxy)silane (M2).

[0502] The silane compound used is shown in Table 2, and the physical properties of the obtained toner particles 27 are shown in Table 3.

[0503] Production Example of Toner Particles 28

[0504] Then, toner particles 28 were obtained in the same manner as in the production example of toner particles 1, except that 0.03 parts of silica particles (Snowtex PS (manufactured by Nissan Chemical Corporation)) were added in the preparation of the polymerizable monomer composition 1 in the production example of toner particles 1, and except that 3-methacryloxypropyltrimethoxysilane (M1) was not added in the polymerization step B.

[0505] The physical properties of the obtained toner particles 28 are given in Table 3.

[0506] [Table 2]

[0507]

[0508] [Table 3]

[0509]

[0510] In the table, *1 represents the normalized intensity of silicon ions (m / z 28) for each toner particle in a time-of-flight secondary ion mass spectrometer (TOF-SIMS). In addition, *2 represents the normalized intensity of silicon ions (m / z 28) after sputtering the toner particles under the above-mentioned condition (A).

[0511] The heading "Presence / Absence of Condensation" indicates whether or not the toner particles contain a condensation product of an organosilicon compound.

[0512] Regarding normalized intensity, for example, the expression “2.11.E-03” herein means “2.11×10 -3 ”.

[0513] Production Example of Toner 1

[0514] Preparation of toner particle dispersion

[0515] Toner particles 1 are re-slurried with ion-exchanged water to obtain a toner particle dispersion 1 having a toner particle concentration of 20% by mass.

[0516] Addition of polyacid metal salt fine particles

[0517] The following materials were weighed into a reaction vessel and mixed using a propeller stirring blade.

[0518] 0.9 parts of sodium phosphate (dodecahydrate)

[0519] 1.0 part of titanium lactate (TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0520] 1500.0 parts of toner particle dispersion

[0521] Next, the pH of the obtained mixed solution was adjusted to 7.0, the temperature of the mixed solution was adjusted to 55° C., and then the mixed solution was maintained for 1 hour while being mixed using a propeller-type stirring blade.

[0522] Thereafter, the pH was adjusted to 9.5 using a 1 mol / L NaOH aqueous solution, and the temperature was maintained at 50° C. for 2 hours with stirring.

[0523] Then, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, stirred for 1 hour, and then filtered and dried while washing with ion-exchanged water. Then, the obtained finely pulverized powder was classified with a multi-stage classifier relying on the wall adhesion effect to obtain colorant 1.

[0524] The number average particle size of the titanium phosphate compound was 11 nm in SEM observation, and the abundance of the titanium phosphate compound was calculated by X-ray fluorescence and found to be 0.2 parts per 100 parts of the toner particles.

[0525] Table 4 shows the physical properties of the obtained Toner 1.

[0526] Production Examples of Toners 2 to 5, 9 to 18, 21 to 31, 35 to 37, 39, and 40

[0527] 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 Production Example of Toner 1, except that the kind of toner particles, the number of parts of the polyacid source, and the kind and number of parts of the metal source were changed as given in Table 4. The amount of polyacid metal salt fine particles present on the surface of each of the obtained toners is given in Table 4.

[0528] Table 4 shows the physical properties of the obtained toner.

[0529] Production Example of Toner 6

[0530] Toner 6 was obtained by adding 0.5 parts of titanium oxide fine particles as a metal source to 100.0 parts of Toner Particles 1, and mixing the whole using an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.).

[0531] Table 4 shows the physical properties of the obtained Toner 6.

[0532] Production Examples of Toners 7, 8, 32, 33, and 38

[0533] Toners 7, 8, 32, 33, and 38 were obtained in the same manner as in the production example of Toner 6, except that the kinds and amounts of toner particles and metal sources were changed as given in Table 4.

[0534] Table 4 shows the physical properties of the obtained toner.

[0535] Production Example of Toner 19

[0536] 100.0 parts of ion exchange water

[0537] 4.8 parts sodium sulfate

[0538] The above substances were mixed, and then 10.0 parts of titanium lactate (TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added while stirring at room temperature at 13,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) The pH was adjusted to 7.0 by adding 1 mol / L hydrochloric acid.

[0539] Thereafter, the solid portion was recovered by centrifugation. Thus, the process of redispersion in ion-exchanged water and recovery of the solid portion by centrifugation was repeated three times to remove ions such as sodium. The resulting product was redispersed in ion-exchanged water and dried by spray drying, thereby obtaining titanium sulfate compound fine particles 1 having a number average particle diameter of 99 nm.

[0540] Then, 0.5 parts of the titanium sulfate compound fine particles 1 are added to 100.0 parts of the toner particles 1, and the whole is mixed using an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), whereby Toner 19 is obtained.

[0541] Table 4 shows the physical properties of Toner 19 obtained.

[0542] Production Example of Toner 20

[0543] 100.0 parts of ion exchange water

[0544] 3.6 parts of sodium carbonate

[0545] The above substances were mixed, and then 10.0 parts of titanium lactate (TC-310, manufactured by Matsumoto Fine Chemical Co., Ltd.) was added while stirring at room temperature at 13,000 rpm using a TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) The pH was adjusted to 7.0 by adding 1 mol / L hydrochloric acid.

[0546] Thereafter, the solid portion was recovered by centrifugation. Thus, the process of redispersion in ion-exchanged water and recovery of the solid portion by centrifugation was repeated three times to remove ions such as sodium. The resulting product was redispersed in ion-exchanged water and dried by spray drying, thereby obtaining titanium carbonate compound fine particles 1 having a number average particle diameter of 91 nm.

[0547] Then, 0.5 parts of the titanium carbonate compound fine particles 1 were added to 100.0 parts of the toner particles 1, and the whole was mixed using an FM mixer (Nippon Coke & Engineering Co., Ltd.) to obtain Toner 20 .

[0548] Table 4 shows the physical properties of the obtained Toner 20.

[0549] Production Example of Toner 34

[0550] Here, 0.5 parts of silica was added to 100.0 parts of Toner Particles 1 , and the whole was mixed using an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) to obtain Toner 34 .

[0551] [Table 4]

[0552]

[0553] In the table, DA represents the number average particle diameter of the polyacid metal salt fine particles. In addition, X represents the amount of the polyacid metal salt fine particles relative to 100 parts of the toner particles.

[0554] Example 1

[0555] First, an electrophotographic apparatus was prepared in the form of a modified laser beam printer LBP652C from Canon Inc. This printer was modified to be connected to an external high voltage power supply and to provide an arbitrary potential difference between the charging blade and the charging roller; furthermore, the process speed was set to 200 mm / sec.

[0556] Next, for the purpose of acclimation to the measurement environment, the process cartridge filled with the toner 1 and the electrophotographic apparatus, which is a cartridge of LBP652C, were left to stand in a normal temperature and normal humidity environment (25° C. / 50% RH) for 48 hours.

[0557] Evaluation of charge retention

[0558] First, the potential difference between the charging blade and the charging roller was set to -400 V and a solid black image was output. During image formation, the printer was stopped, the process cartridge was removed from the printer body, and the charge amount of the toner on the photosensitive drum was evaluated using a charge amount distribution measuring device, E-SPARTAnalyzer EST-1 (manufactured by Hosokawa Micron Corporation).

[0559] The charge retention was evaluated by comparing the charge amount on the developing roller in the above-mentioned charge injection evaluation and the charge amount on the photosensitive drum in this evaluation.

[0560] In this evaluation, the higher the charge retention, the less likely it is that charge leakage will occur during the development step, and thus, as a result, a higher charge amount will be retained. That is, the smaller the numerical value of the evaluation, the better the charge retention.

[0561] The evaluation results of Example 1 are given in Table 5.

[0562] Charge retention

[0563] A: The difference between the charge on the developing roller and the photosensitive drum is 3μC / g or less

[0564] B: The difference between the charge amount on the developing roller and the photosensitive drum is greater than 3 μC / g and less than 6 μC / g

[0565] C: The difference between the charge amount on the developing roller and the photosensitive drum is greater than 6 μC / g and less than 10 μC / g

[0566] D: The difference between the charge on the developing roller and the photosensitive drum is greater than 10μC / g

[0567] Charge injection properties (injected charge)

[0568] First, a solid white image was output with the potential difference between the charging blade and the charging roller set to 0 V. The printer was stopped during image formation, the process cartridge was removed from the printer body, and the charge amount and charge amount distribution of the toner on the developing roller were evaluated using a charge amount distribution measuring device, E-SPART Analyzer EST-1 (Hosokawa Micron Corporation).

[0569] Next, the potential difference between the charging blade and the charging roller was set to -400 V, and the same evaluation was performed.

[0570] The injected charge amount and the injected charge amount distribution were evaluated based on the change ΔQ / M (unit: μC / g) in charge amount when the potential difference was 0 V and −400 V and the change in charge amount distribution.

[0571] The evaluation standard of the charge amount distribution is the multiple of the half-value width of the charge amount distribution at -400 V relative to the half-value width of the charge amount distribution at 0 V.

[0572] Under this standard, a smaller multiple indicates a narrower charge amount distribution and a better charge state.

[0573] In this evaluation, the higher the charge injection property, the greater the change in charge amount with respect to the potential difference, and therefore the greater the charge amount difference (ΔQ / M). At the same time, a uniform charge amount distribution can be achieved, which is one of the excellent injection charging characteristics.

[0574] The evaluation results of Example 1 are given in Table 5.

[0575] Charge injection

[0576] A: ΔQ / M is greater than 20μC / g

[0577] B: ΔQ / M is greater than 10μC / g and less than 20μC / g

[0578] C: ΔQ / M greater than 5μC / g and less than 10μC / g

[0579] D: ΔQ / M is less than 5μC / g

[0580] Injection charge distribution

[0581] A: The half-value width of the charge distribution at -400V is less than 0.70 times that at 0V

[0582] B: The half-value width of the charge distribution at -400V is greater than 0.70 times and less than 0.80 times that at 0V

[0583] C: The half-value width of the charge distribution at -400V is greater than 0.80 times and less than 0.90 times that at 0V

[0584] D: The half-value width of the charge distribution at -400V is greater than 0.90 times that at 0V

[0585] Evaluation of charge injection properties (injected charge amount) at low voltage

[0586] Evaluation was performed under similar conditions to the above-mentioned evaluation of charge injectability, except that the potential difference between the charging blade and the charging roller was changed to -200 V.

[0587] The injected charge amount and the injected charge amount distribution were evaluated based on the change ΔQ / M (unit: μC / g) in charge amount when the potential difference was 0 V and −200 V and the change in charge amount distribution.

[0588] In this evaluation, a larger charge amount difference ΔQ / M (unit: μC / g) between the potential difference cases of 0 V and −200 V indicates better charge injection properties and higher charge amount even at a low voltage.

[0589] The evaluation results of Example 1 are given in Table 5.

[0590] Charge injection at low voltage

[0591] A: ΔQ / M is greater than 20μC / g

[0592] B: ΔQ / M is greater than 10μC / g and less than 20μC / g

[0593] C: ΔQ / M greater than 5μC / g and less than 10μC / g

[0594] D: ΔQ / M is less than 5μC / g

[0595] Examples 2 to 40, Comparative Examples 1 to 6

[0596] Evaluation was performed in the same manner as in Example 1, except that the toner charged was changed as given in Table 5. The evaluation results are given in Table 5.

[0597] [Table 5]

[0598]

[0599] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A toner comprising toner particles containing a binder resin, It is characterized in that The toner particles include a condensation product of an organosilicon compound, In the time-of-flight secondary ion mass spectrometry TOF-SIMS of the toner particles, The normalized intensity of the silicon ion with m / z of 28 given by the following formula (I) derived from the condensation product of the organosilicon compound was 7.00×10 -4 to 3.00×10 -2 ; Normalized intensity of silicon ions with m / z 28 = {ionic intensity of silicon ions with m / z 28} / {total ionic intensity of m / z 0.5 to 1850} (I), The normalized intensity of silicon ions with m / z 28 by time-of-flight secondary ion mass spectrometry after sputtering the toner particles by Ar gas cluster ion beam Ar-GCIB under the following conditions (A) was 6.99×10 -4 the following; (A) Acceleration voltage: 5 kV, current: 6.5 nA, grating size: 600 × 600 μm, irradiation time: 5 sec / cycle, sputtering time: 250 sec, The toner includes fine particles on the surfaces of the toner particles, and The fine particles have at least one selected from the group consisting of polyacid metal salt fine particles which are reaction products of a compound containing at least one of Ti and Al elements and a polyacid, strontium titanate fine particles, titanium oxide fine particles, and aluminum oxide fine particles.

2. The toner according to claim 1, The normalized intensity of the silicon ion with m / z of 28 given by the formula (I) derived from the condensation product of the organosilicon compound is 7.00×10 -4 to 8.00×10 -3 ,and The normalized intensity of silicon ions with m / z of 28 by time-of-flight secondary ion mass spectrometry after sputtering the toner particles under the condition (A) was 6.00×10 -4 the following. 3 . The toner according to claim 1 , wherein the fine particles are polyacid metal salt fine particles that are a reaction product of a compound containing at least one of Ti and Al elements and a polyacid. 4 . The toner according to claim 3 , wherein the polyacid of the polyacid metal salt fine particles is phosphoric acid. 5 . The toner according to claim 3 , wherein the metal element in the polyacid metal salt fine particles is Ti. 6 . The toner according to claim 1 , wherein a total content of Ca and Mg elements in the toner particles measured by inductively coupled plasma atomic emission spectrometry is 23 μmol / g or less.

7. The toner according to claim 1 or 2, wherein the condensation product of the organic silicon compound is a silane-modified resin R having a structure represented by the following formula (1); In formula (1), P 1 Indicates the polymer part; L 1 Represents a single bond or a divalent linking group; R 1 to R 3 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a hydroxyl group; and m represents a positive integer; when m is equal to or greater than 2, multiple L 1 , multiple R 1 , multiple R 2 and multiple R 3 are the same or different; however, Si is bonded to at least one carbon, and R 1 to R 3 At least one of them is condensed with the organosilicon compound.

8. The toner according to claim 7, wherein the R 1 to R 3 At least one of them represents an alkoxy group having 1 or more carbon atoms, or a hydroxy group.

9. The toner according to claim 7, wherein the R 1 to R 3 The groups that do not condense with the organosilicon compound each independently represent an alkoxy group having 1 or more carbon atoms or a hydroxyl group.

10. The toner according to claim 7, wherein the P 1 Indicates a styrene acrylic resin portion or a polyester resin portion.

11. The toner according to claim 7, wherein the L 1 It is represented by the following formula (2); In formula (2), R 5 represents a single bond, an alkylene group or an arylene group; (*) represents the P of formula (1) 1 (**) represents the bonding site with the silicon atom in formula (1). 12 . The toner according to claim 1 , wherein the content of the fine particles is 0.10 parts by mass to 0.30 parts by mass relative to 100 parts by mass of the toner particles. 13 . The toner according to claim 1 , wherein the polyacid metal salt fine particles have a number average particle diameter DA of 5 nm to 30 nm.

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