Toner and toner manufacturing method

Abstract

To provide a toner excellent in low-temperature fixability, heat-resistant storage properties and ejected paper adhesion properties in a high-temperature and high-humidity environment, and capable of forming a high-quality image when used in a low-temperature and low-humidity environment; and to provide a method for manufacturing the toner.SOLUTION: Provided is a toner with toner particles having a resin A and a resin B. A method for manufacturing the toner includes: a step for obtaining the toner in which the resin A has a structure represented by a prescribed general formula and the resin B has a monomer unit represented by a prescribed general formula, and toner slurry by having toner base particles containing the resin B dispersed in an aqueous medium; and a step for inputting a monomer composition containing a monomer represented by a prescribed general formula and a radical polymerization initiator to the obtained toner slurry, and forming the resin A on the surfaces of the toner base particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a toner used in electrophotography, electrostatic recording, and toner jet recording, and a method for producing the toner. [Background technology]

[0002] In recent years, there has been a demand for energy conservation in various electrophotographic processes in order to reduce power consumption. A large proportion of the power consumed by laser beam printers comes from the thermal energy of the fuser used in the toner fixing process, and efforts have been made to reduce power consumption by lowering the fixing temperature. An effective way to lower the fixing temperature is to improve the low-temperature fixability of the toner. On the other hand, toners are also required to have storage stability (heat-resistant storage stability) so that they can withstand high-temperature storage environments. In order to achieve both low-temperature fixability and heat-resistant storage stability of toners, a method has been studied in which a side-chain crystalline resin with a melting point of 50.0°C to 90.0°C is used as a binder resin (Patent Document 1). Patent Document 1 also describes that the image loading ability is good. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-130243 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when continuous double-sided printing at a high printing rate was performed using the toner described in Patent Document 1 in a high-temperature, high-humidity environment, it was found that the paper stacked on the paper output tray was sometimes soiled and the paper output adhesion (image loading ability) was sometimes insufficient. It was also found that such a toner was prone to charge-up in a low-temperature, low-humidity environment, which could result in image defects such as fogging. The toner and the method for producing the toner according to the present disclosure are excellent in low-temperature fixability, heat-resistant storage stability, and adhesiveness at discharged paper in a high-temperature, high-humidity environment, and are capable of forming high-quality images when used in a low-temperature, low-humidity environment, and the method for producing the toner is also provided. [Means for solving the problem]

[0005] The toner of the present disclosure is Resin B Toner base particles containing Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2): do It is characterized by:

[0006] [ka]

[0007] In formula (1), P 1 represents the polymer moiety, and R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L 1 denotes an alkylene group with 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NH-R 6 -**, where * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; Multiple L when m is 2 or more 1 , multiple R1 , multiple R 2 and multiple R 3 may be the same or different.

[0008] [ka]

[0009] In formula (2), R 4 represents a hydrogen atom or a methyl group, and n is 1. 7 ~ 29 Represents an integer. The present disclosure also provides: Resin B Toner base particles containing Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B is a monomer unit represented by the following formula (2): and a monomer unit represented by the following formula (3): With do It is characterized by: TIFF0007753475000003.tif28170 In formula (1), P 1 represents the polymer moiety, and R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L 1 denotes an alkylene group with 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NH-R 6 -**, where * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; Multiple L when m is 2 or more 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different. TIFF0007753475000004.tif35170 In formula (2), R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 11 to 35. TIFF0007753475000005.tif24170 In formula (3), R 7 represents a hydrogen atom or a methyl group. Furthermore, the present disclosure provides Resin B Toner base particles containing Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2): When the content of the resin A in the toner particles is MA (mass%) and the content of the resin B in the toner particles is MB (mass%), MA / MB is 0.0050≦[MA / MB]≦0.2000 is It is characterized by: TIFF0007753475000006.tif28170 In formula (1), P 1 represents the polymer moiety, and R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L 1 denotes an alkylene group with 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NH-R 6 -**, where * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; Multiple L when m is 2 or more 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different. TIFF0007753475000007.tif35170 In formula (2), R 4 represents a hydrogen atom or a methyl group, and n is 1. 1 ~ 35 Represents an integer. [Effects of the Invention]

[0010] According to the present disclosure, it is possible to provide a toner that has excellent low-temperature fixability, heat-resistant storage stability, and paper discharge adhesion in a high-temperature, high-humidity environment, and that is capable of forming high-quality images when used in a low-temperature, low-humidity environment, and a method for manufacturing the toner. DETAILED DESCRIPTION OF THE INVENTION

[0011] In the present invention, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. The monomer unit refers to the reacted form of a monomer substance in a polymer.

[0012] The toner of the present disclosure will be specifically described below. The toner of the present disclosure is A toner having toner particles having a resin A and a resin B, The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2): It is characterized by:

[0013] [ka]

[0014] In formula (1), P 1 represents the polymer moiety, and R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L 1 denotes an alkylene group with 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NH-R 6 -**, where * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; Multiple L when m is 2 or more 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different.

[0015] [ka]

[0016] In formula (2), R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 11 to 35.

[0017] The toner having the above characteristics has excellent low-temperature fixability, heat-resistant storage stability, and adhesiveness to discharged paper in a high-temperature, high-humidity environment, and is capable of forming high-quality images even when used in a low-temperature, low-humidity environment. The inventors believe that the effects are manifested for the following reasons. Resin B has a monomer unit represented by formula (2). The monomer unit represented by formula (2) has a high degree of freedom in the molecular chain and is likely to lower the glass transition temperature (Tg) of the resin during fixing, thereby improving low-temperature fixing properties. However, when a resin having a monomer unit represented by formula (2) is used, the Tg of the fixed image is likely to decrease. Therefore, when the paper is stacked on the paper output tray in a heated state immediately after ejection, it is thought that the heat and pressure from the paper's own weight make it more likely for the paper to stick together after ejection.

[0018] The carbonyl groups in resin A and the ester groups in resin B have a high affinity, and it is thought that resins A and B tend to be spatially close together in the fixed toner. If resins A and B are brought even closer together within the spatial arrangement described above, the silane moieties in resin A and the long-chain alkyl moieties in resin B have a low affinity, so the long-chain alkyl moieties in resin B tend to gather locally, and the gathered long-chain alkyl moieties tend to be oriented in microscopic regions. This is thought to result in the formation of domains within the toner particles. The formed domains restrict the movement of molecules, so that the decrease in Tg of the image can be suppressed. 1 is an alkylene group having 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NHR 6 -** (* represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each independently an alkylene group having 8 or less carbon atoms, and each carbon may have a hydroxyl group as a substituent.) the distance between the carbonyl group of resin A and the silane moiety is short, which is thought to make the above-mentioned effect more pronounced and thereby achieve the effect of the present disclosure.

[0019] Resin A will be described in detail below. Resin A has a structure represented by the following formula (1).

[0020] [ka]

[0021] In formula (1), P 1 represents the polymer moiety, and R 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L 1 denotes an alkylene group with 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NH-R 6 -**, where * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; Multiple L when m is 2 or more 1 , multiple R 1 , multiple R 2 and multiple R 3 may be the same or different.

[0022] L in formula (1) 1 is an alkylene group having 8 or less carbon atoms, *-O-**, *-OR 5 -**, *-NH-**, *-NHR 6 -** (* represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R 5 , R 6 are each alkylene groups having 8 or less carbon atoms, and each carbon may have a hydroxyl group as a substituent. When Furthermore, resins having a monomer unit represented by formula (2) tend to accumulate charge in low-temperature, low-humidity environments, which can lead to charge-up and image defects such as fogging. The toner particles according to the present disclosure contain resin B having a monomer unit represented by formula (2) and resin A having a structure represented by formula (1), which, as described above, makes it easy for resin A and resin B to be spatially close to each other. This facilitates transfer of charge from resin B to the carbonyl group of resin A via the ester moiety of resin B, thereby suppressing charge-up in low-temperature, low-humidity environments. This suppresses image defects such as fogging, improving image quality. L in equation (1) 1 *-NHR 6 -** is preferred. 1 Ga*-NHR 6 In the case of -**, the above-mentioned effect is easily exhibited and the adhesiveness of discharged paper is easily improved. Image quality is easily improved. 6 The alkylene group represented by the formula (I) preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. In addition, in the resin A, L 1 *-OR 5 -** is also preferable because the effects of the present disclosure are easily achieved. 5 The group preferably has 1 to 4 carbon atoms, and more preferably has 1 to 3 carbon atoms. Furthermore, L 1 When is an alkylene group, the alkylene group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0023] R in formula (1) 1 ~R 3 each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R 1 ~R 3 At least one of R represents an alkoxy group or a hydroxy group having one or more carbon atoms. 1 ~R 3Among the substituents that can be represented, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 4. The number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2.

[0024] R in formula (1) 1 ~R 3 To make one or more of R into a hydroxy group, 1 ~R 3 Resin A in which one or more of the above groups are alkoxy groups may be hydrolyzed to convert the alkoxy groups into hydroxy groups. Any method for hydrolysis may be used, but examples include the following. R in the formula (1) 1 ~R 3 Resin A, in which one or more of the above groups are alkoxy groups, is dissolved or suspended in a suitable solvent (which may be a polymerizable monomer), and the pH is adjusted to acidic using an acid or alkali, followed by mixing and hydrolysis. Further, hydrolysis may be caused during the production of toner particles.

[0025] Any method may be used to form the structure represented by formula (1), but examples include the following methods. It can be formed by a method of reacting a carboxyl group in a resin with an aminosilane coupling agent, a method of polymerizing an ethylenically unsaturated bond site in a resin or a monomer having an ethylenically unsaturated bond with a (meth)acrylic silane coupling agent, a method of reacting a hydroxyl group in a resin with an isocyanate silane coupling agent, or a method of reacting an isocyanate group in a resin with an aminosilane coupling agent. Examples of the aminosilane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyldimethoxymethylsilane. Examples of the (meth)acrylic silane coupling agent include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-acryloxyoctyltriethoxysilane, 8-methacryloxyoctyltriethoxysilane, 3-[acrylate (triethoxysilyl)methyl, 3-methacrylate (triethoxysilyl)methyl, 3-[dimethoxy(methyl)silyl]propyl, 3-[dimethoxy(methyl)silyl]propyl, acrylate [dimethoxy(methyl)silyl]methyl, methacrylate [dimethoxy(methyl)silyl]methyl, 3-(methacryloyloxy)propyltris(trimethylsilyloxy)silane, and the like. Examples of the isocyanate coupling agent include isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropylmethyldimethoxysilane.

[0026] The content of the structure represented by the following formula (4) in the resin A is preferably 0.5% by mass or more and 10.0% by mass or less. When it is 0.5% by mass or more, the adhesiveness of discharged paper and the low-temperature and low-humidity Image quality at low temperatures and low humidity is likely to improve. When the content is 10.0% by mass or less, the hydrophilicity of the entire resin can be prevented from increasing due to an excess of silane moieties in resin A, and the spatial arrangement of resin A and resin B described above is not hindered, so that discharged paper adhesion and image quality at low temperatures and low humidity are likely to improve. A more preferred range is 1.0% by mass or more and 7.0% by mass or less. The content of the structure represented by formula (4) in resin A can be controlled by adjusting the amount of silane coupling agent added and the amount of functional groups with which the silane coupling agent reacts.

[0027] [ka]

[0028] In formula (4), R 1 ~R 3 is R in equation (1). 1 ~R 3 is the same as L 1 is L in equation (1). 1 is the same as:

[0029] The weight-average molecular weight MwA of resin A is preferably 8,000 or more and 50,000 or less. When it is 8,000 or more, the amount of low-molecular-weight components tends to be reduced, and thus heat-resistant storage stability tends to be improved. When MwA is 50,000 or less, molecular mobility is high after fixing, and spatial arrangement is facilitated, and therefore paper discharge adhesion tends to be improved. MwA is more preferably 12,000 or more and 30,000 or less. MwA can be controlled by changing the resin reaction temperature, reaction time, monomer composition, initiator amount, etc.

[0030] P in the formula (1) 1 Examples of the resin moiety include, but are not limited to, polyester resin moieties, vinyl resin moieties, polyurethane resin moieties, polyurea resin moieties, polycarbonate resin moieties, phenol resin moieties, polyolefin resin moieties, and epoxy resin moieties. Among these, P in the resin A 1 It is preferable that the resin composition contains a polyester resin moiety or a vinyl resin moiety, since this tends to improve adhesiveness at discharge. For example, the resin composition may be a hybrid resin moiety of a polyester resin and a vinyl resin.

[0031] Polymerizable monomers that can be used to produce the polyester resin portion include polycarboxylic acids and polyhydric alcohols. Examples of polycarboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexane dicarboxylic acid. Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, isosorbide, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

[0032] Vinyl monomers that can be used to manufacture the vinyl resin portion include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, Examples of the acrylates include sil acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-hydroxyethyl acrylate, 2-benzoyloxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl phosphate ethyl methacrylate, 2-hydroxyethyl methacrylate, dibutyl phosphate ethyl methacrylate, maleic acid, acrylic acid, and methacrylic acid.

[0033] The resin A may further have a monomer unit represented by the following formula (3).

[0034] [ka]

[0035] In formula (3), R 7 represents a hydrogen atom or a methyl group. When the resin A has a monomer unit represented by formula (3), image quality in a low-temperature, low-humidity environment is likely to improve. The method for introducing the monomer unit represented by formula (3) into resin A is not particularly limited, but examples include a method using acrylonitrile or methacrylonitrile as one of the polymerizable monomers capable of forming resin A. The monomer unit represented by formula (3) preferably accounts for 5.0 to 60.0% by mass in resin A.

[0036] Resin A is polymerized and added during the production of toner particles, and is also used in the following manufacturing processes: The method for introducing the compound into the toner particles may be, but is not limited to, the above methods. a step of dispersing toner base particles containing resin B in an aqueous medium to obtain a toner slurry; a step of adding a monomer composition containing a monomer represented by the following formula (6) and a radical polymerization initiator to the obtained toner slurry to form the resin A on the surfaces of the toner base particles; Resin A can also be introduced into toner particles via a method having the following formula:

[0037] [ka]

[0038] In formula (6), R 8 represents a hydrogen atom or a methyl group.

[0039] Formula (1) is preferably at least one selected from the group consisting of structures represented by the following formulas (7) to (12).

[0040] [ka]

[0041] R in equations (8) to (12) 1 ~R 3 ,R 5 ~R6 is R in equation (1). 1 ~R 3 ,R 5 ~R 6 and R 7 represents a hydrogen atom or a methyl group, and R in formulas (9) and (10) 9 , R 10 represents an alkylene group having 1 to 6 carbon atoms (preferably 1 to 4), and P in formulas (11) and (12) 2 represents the main chain skeleton of the polyester resin. The structure represented by formula (11) is not particularly limited, but specific examples include structures such as those shown in the following formulas (13) and (14). The structure represented by formula (12) is not particularly limited, but specific examples include structures such as those shown in formulas (15) and (16).

[0042] [ka]

[0043] [In formulas (13) to (16), R 1 ~R 3 ,R 6 is R in equation (1). 1 ~R 3 ,R 6 where X represents a residue obtained by removing a carboxy group from a polycarboxylic acid, and Y represents a residue obtained by removing a hydroxy group from a polyhydric alcohol. The residue obtained by removing a carboxy group from a polycarboxylic acid and the residue obtained by removing a hydroxy group from a polyhydric alcohol can be obtained by condensing the above-mentioned polymerization monomers that can be used to produce the polyester resin segment.] Each of X and Y may be one type of structure or multiple types of structures. Among these, X is preferably at least one selected from the group consisting of an alkylene group (preferably having 1 to 12 carbon atoms), an alkenylene group (preferably having 2 to 4 carbon atoms), and a phenylene group (preferably having 6 to 12 carbon atoms). Y is preferably at least one selected from the group consisting of an alkylene group (preferably having 1 to 12 carbon atoms), a phenylene group (preferably having 6 to 12 carbon atoms), and a structure represented by the following formula (17).

[0044] [ka]

[0045] In formula (17), R 11 represents an ethylene group or a propylene group. x and y are each an integer of 0 or more, and the average value of x+y is 2 to 10. In formula (17), *** represents a bond to an oxygen atom in formulas (13) to (16).

[0046] Resin B will be described in detail. Resin B has a monomer unit represented by formula (2).

[0047] [ka]

[0048] In formula (2), R 4 represents a hydrogen atom or a methyl group, and n represents an integer of 11 to 35. In formula (2), when n is 11 or more, a plasticizing effect is exhibited during fixing, improving low-temperature fixability. When n is 35 or less, charging properties are improved in low-temperature, low-humidity environments, resulting in high-quality images. The preferred range for n is 17 or more and 29 or less, and the more preferred range is 17 or more and 21 or less.

[0049] The content of the monomer unit represented by formula (2) in resin B is preferably 5.0% by mass or more and 95.0% by mass or less. Within this range, it is easy to achieve both low-temperature fixability and image quality in a low-temperature, low-humidity environment. The content is more preferably 8.0% by mass or more and 80.0% by mass or less.

[0050] As a method for introducing the monomer unit represented by formula (2) into resin B, for example, there is a method of polymerizing a vinyl monomer or a resin containing an ethylenically unsaturated bond with a monomer such as the following. Examples of monomers for introducing the monomer unit represented by formula (2) into Resin B include dodecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, hexadecyl (meth)acrylate, lauryl (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

[0051] Resin B preferably has a monomer unit represented by the following formula (3). [ka]

[0052] In formula (3), R 7 represents a hydrogen atom or a methyl group. When resin B has a monomer unit represented by formula (3), the monomer unit represented by formula (2) more easily forms a domain, and therefore discharged paper adhesion and heat-resistant storage stability are more likely to be improved. The method for introducing the monomer unit represented by formula (3) into resin B is not particularly limited, and examples thereof include a method of polymerizing at least one selected from the group consisting of acrylonitrile and methacrylonitrile with an ethylenically unsaturated bond in resin B, and a method of polymerizing a monomer having an ethylenically unsaturated bond with at least one selected from the group consisting of acrylonitrile and methacrylonitrile. The content of the monomer unit represented by formula (3) in resin B is preferably 5.0 to 60.0% by mass.

[0053] The weight-average molecular weight MwB of Resin B is preferably 15,000 or more and 250,000 or less. When MwB is 15,000 or more, the amount of low-molecular-weight components tends to be reduced, and thus heat-resistant storage stability tends to be improved. When MwB is 100,000 or less, deformation during fixing tends to occur, and thus low-temperature fixability tends to be improved. A more preferred range for MwB is 20,000 or more and 80,000 or less. MwB can be controlled by changing the reaction temperature, reaction time, monomer charging ratio, initiator amount, etc. when producing Resin B.

[0054] Resin B is not particularly limited as long as it has a monomer unit represented by formula (2), and known resins such as vinyl resins, polyester resins, and epoxy resins can be used. Among these, resin B is preferably a vinyl resin. Examples of vinyl resins include polymers of monomers containing ethylenically unsaturated bonds. Examples of vinyl-based monomers that can be used to produce the vinyl resin include monomers that can be used in the vinyl resin portion of resin A described above.

[0055] The method for introducing resin B into toner particles is not particularly limited, but examples thereof include adding synthesized resin B during the production of toner particles, as well as the following methods. a step of dispersing and suspending a polymerizable monomer composition for obtaining resin B in water and polymerizing the polymerizable monomer composition to obtain resin B; a step of dispersing the toner base particles containing the resin B in an aqueous medium to obtain a toner slurry; a step of adding a monomer composition containing a monomer represented by the following formula (6) and a radical polymerization initiator to the obtained toner slurry to form the resin A on the surfaces of the toner base particles; A method having the following.

[0056] [ka]

[0057] In formula (6), R 8 represents a hydrogen atom or a methyl group.

[0058] The toner particles will be described in detail below. The SP value of resin A measured by the Fedors method is SPA [(J / m 3 ) 0.5 ], and the SP value of resin B in the Fedors method is SPB[(J / m 3 ) 0.5 ], then │SPA-SPB│≦2.00[(J / m 3 ) 0.5 ]. |SPA-SPB|≦2.00[(J / m 3 ) 0.5 In the case of [SPA-SPB], resin A and resin B are more likely to be spatially arranged after fixing, and therefore the effect of improving the adhesiveness of discharged paper is more likely to be realized. A more preferable range is |SPA-SPB|≦1.00 [(J / m 3 ) 0.5 SPA and SPB can be controlled by changing the compositions of resins A and B. The lower limit of |SPA-SPB| ​​is not particularly limited, but is, for example, 0.00 or more. The SPA is preferably 19.00 [(J / m 3 ) 0.5 ]~23.00[(J / m 3 ) 0.5 SPB is preferably 18.00 [(J / m 3 ) 0.5 ]~23.00[(J / m 3 ) 0.5 ].

[0059] When the content of resin A in the toner particles is MA (mass%) and the content of resin B in the toner particles is MB (mass%), it is preferable that MA / MB is 0.0050≦MA / MB≦0.2000. When 0.0050≦MA / MB, paper discharge adhesion is likely to be improved. When MA / MB≦0.2000, heat-resistant storage stability is likely to be improved. MA / MB is more preferably 0.0050≦MA / MB≦0.1000. The content MA of the resin A in the toner particles is preferably 0.40% by mass to 4.0% by mass. Furthermore, the content MB of resin B in the toner particles is preferably 40.0% by mass to 90.0% by mass.

[0060] In measurements of the surfaces of toner particles using a time-of-flight secondary ion mass spectrometer (TOF-SIMS), the ion count derived from silicon with a mass number of 28 relative to the total ion count in mass numbers of 1 to 1800 is preferably 0.0010 to 0.0050, and more preferably 0.0020 to 0.0040. When the silicon-derived ion count is 0.0010 to 0.0050, it is believed that resin A is located near the surface of the toner particles. The phenomenon of discharged paper adhesion is thought to be greatly influenced by the melting of the toner surface. Therefore, when resin A is located near the surface of the toner particles, it is thought that the effect of suppressing discharged paper adhesion as described above is more likely to be realized. Methods for controlling the silicon-derived ion count include changing the composition and amount of resin A added, as well as changing the manufacturing method of the toner particles for introducing the aforementioned resin A.

[0061] The toner particles may contain a release agent. Examples of the release agent include aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes, block copolymers of aliphatic hydrocarbon waxes, waxes mainly composed of fatty acid esters, partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax, partially esterified products of fatty acids and polyhydric alcohols, methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats, and Fischer-Tropsch wax. The content of the release agent in the toner particles is preferably 1.50% by mass or more and 20.0% by mass or less.

[0062] A method for producing toner particles will now be described. The toner particles can be produced by known methods, for example, a suspension polymerization method in which a polymerizable monomer composition containing a polymerizable monomer for obtaining resin B, resin A or a polymerizable monomer for obtaining resin A, and a release agent, if necessary, is suspended and granulated in an aqueous medium, and the polymerizable monomer in the polymerizable monomer composition is polymerized; A kneading and grinding method in which various toner constituent materials such as resin B, resin A, and optionally a release agent are kneaded, ground, and classified; An emulsion aggregation method in which a dispersion of resin B and resin A is emulsified and dispersed, and the dispersion is mixed with a dispersion of a release agent or the like as needed, followed by aggregation and heat fusion to obtain toner particles; An emulsion polymerization aggregation method in which a dispersion formed by emulsion-polymerizing a polymerizable monomer constituting resin B is mixed with a dispersion obtained by emulsifying and dispersing resin A and, if necessary, a dispersion of a release agent, etc., followed by aggregation and heat fusion to obtain toner particles; An organic solvent dispersion containing resin B, resin A, and optionally a release agent, etc., is added to water. Dissolution suspension method in which the drug is suspended in a system medium and granulated; etc. can be used.

[0063] Alternatively, the toner can be produced by the following production method. a step of dispersing the toner base particles containing the resin B in an aqueous medium to obtain a toner slurry; a step of adding a monomer composition containing a monomer represented by the following formula (6) and a radical polymerization initiator to the obtained toner slurry to form the resin A on the surface of the toner base particles; The toner manufacturing method according to the present invention comprises the steps of:

[0064] [ka]

[0065] In formula (6), R 8 represents a hydrogen atom or a methyl group.

[0066] The toner particles may be used as they are, or an external additive may be added to the toner particles to improve the image quality of the toner. Suitable external additives include inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles. These inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof. Furthermore, if necessary, an external additive other than those mentioned above may be added to the toner particles. The amount of the external additive added is preferably 0.5 to 5.0 parts by mass per 100 parts by mass of the toner particles.

[0067] The toner particles may contain a colorant. The colorant is not particularly limited, and the following known colorants can be used, for example. Yellow pigments that can be used include condensed azo compounds such as yellow iron oxide, Nabels Yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, and Tartrazine Lake, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following: CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180, etc. Orange pigments include the following: Permanent Orange GTR, Pyrazolone Orange, Balkan Orange, Benzidine Orange G, Induthrene Brilliant Orange RK, Induthrene Brilliant Orange GK, etc. Examples of red pigments include condensed azo compounds such as red iron oxide, permanent red 4R, lithol red, pyrazolone red, watching red calcium salt, lake red C, lake red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, and alizarin lake, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following: CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 1 84, 185, 202, 206, 220, 221, 254, etc. Examples of blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, copper phthalocyanine compounds such as fast sky blue and indanthrene blue BG, and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following: CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66, etc. Examples of black pigments include carbon black, aniline black, non-magnetic ferrite, magnetite, and pigments toned to black using the above yellow, red and blue colorants. These colorants may be used alone or in combination of two or more, and may also be used in the form of a solid solution. The content of the colorant in the toner particles is preferably 3.0% by mass to 15.0% by mass.

[0068] The toner particles may contain a charge control agent. Known charge control agents can be used as the charge control agent. Charge control agents include those that control the toner to be negatively charged and those that control the toner to be positively charged. Examples of charge control agents that control the toner to be negatively charged include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin-based charge control agents. On the other hand, examples of substances that control the toner to be positively charged include the following. Nigrosine and nigrosine modifications such as fatty acid metal salts; guanidine compounds; imidazole compounds; onium salts such as quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and their analogous phosphonium salts, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin-based charge control agents.

[0069] The methods for measuring the various physical properties of the toner will be described below. <Separation of toner and external additives> First, when the surfaces of the toner particles have been treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles. Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the above concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a 50 mL centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion and break up any clumps of toner with a spatula or similar. The centrifuge tube is shaken at 350 strokes per minute (spm) for 20 minutes. After shaking, the solution is transferred to a 50 mL swing-out rotor glass tube and centrifuged at 3500 rpm for 30 minutes in a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.). This operation separates the toner particles from the detached external additives. Visually check that the toner and aqueous solution have been sufficiently separated, and collect the toner that has separated to the top layer using a spatula. The collected toner is filtered through a vacuum filter and then dried in a dryer for at least an hour to obtain toner particles. This process is repeated multiple times to ensure the required amount.

[0070] <Method for extracting Resin A and Resin B from toner particles> Resin A in the toner particles is extracted by separating the extract using tetrahydrofuran (THF) using a solvent gradient elution method. The preparation method is shown below. Weigh out 10.0 g of toner particles, place them in a cylindrical filter paper (Toyo Roshi No. 84), and place them in a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as the solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble fraction. The THF-soluble fraction contains either Resin A or Resin B. Repeat this process multiple times to obtain the required amount of THF-soluble fraction. The solvent gradient elution method uses a gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire preparative column 50 mm φ 250 mm) with a column temperature of 30 °C, a flow rate of 50 mL / min, and a mobile phase of acetonitrile as a poor solvent and THF as a good solvent. The sample for separation was prepared by dissolving 0.02 g of the THF-soluble fraction obtained by extraction in 1.5 mL of THF. The mobile phase started with a 100% acetonitrile composition, and 5 minutes after sample injection, the THF ratio was increased by 4% per minute until the mobile phase reached 100% THF over 25 minutes. The components were separated by drying the resulting fractions. This yielded Resin A or Resin B. Which fraction is resin A or resin B? 13 It can be distinguished by C-NMR measurement.

[0071] <Measurement of Resin A Content and Resin B Content in Toner Particles> The contents of resin A and resin B in the toner particles can be calculated from the amounts of each resin or polymerizable monomers capable of forming each resin charged when producing the toner particles. In addition, by identifying and extracting resin A and resin B from each fraction obtained by a method for extracting resin A and resin B from toner particles, the respective contents can be calculated for the toner particles subjected to a Soxhlet extractor.

[0072] <How to confirm the structure of Resin A and Resin B> Polymer moiety P in formula (1) of resin A 1 , L 1 Part, R 1 ~R 3 The monomer unit structures in resin B represented by the moiety and formulas (2) and (3) are 1 H-NMR analysis, 13 C-NMR analysis, 29 This is carried out using Si-NMR. The measurement sample is either resin A or resin B itself, or resin A or resin B extracted from toner particles by the above-mentioned extraction method. R in formula (1) 1 ~R 3 The alkoxy group or hydroxy group in 29 The valence of the alkoxy group or hydroxy group relative to the silicon atom can be determined by the method shown in "Si-NMR (solid state) measurement conditions."

[0073] ( 29 Si-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2 mm diameter Sample amount: 150 mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 97.38MHz ( 29 Si) Reference material: DSS (external standard: 1.534ppm) Sample rotation speed: 10kHz Contact time: 10ms Delay time: 2 seconds Accumulation times: 2000 to 8000 times From the above measurement, the abundance ratio of multiple silane components according to the number of oxygen atoms bonded to Si can be determined by peak separation and integration using curve fitting. In this way, the R 1 ~R 3 The valence of the alkoxy group or hydroxy group relative to the silicon atom can be confirmed. P in formula (1) 1 , L 1 and R 1 ~R 3 The structure of the monomer unit in resin B represented by formula (2) and formula (3) is 13 This can be confirmed by C-NMR (solid state) measurement. The measurement conditions are as follows:

[0074] ( 13 C-NMR (solid state) measurement conditions Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2 mm diameter Sample amount: 150 mg Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz ( 13 C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2 seconds Number of times accumulated: 1024 P in formula (1) 1 , L 1 , R 1 ~R 3 The peaks are separated into various types depending on the type of monomer unit in resin B represented by formula (2) and formula (3), and each peak is identified to obtain P 1 , L 1 , R 1 ~R 3 , determining the structures of formulas (2) and (3).

[0075] <Method for measuring weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the polymer, resin or toner particles is measured by gel permeation chromatography (GPC) as follows. First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of components soluble in THF is approximately 0.8% by mass. This sample solution is used for measurements under the following conditions. Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (trade names: "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0076] <Calculation methods of SPA and SPB> SPA and SPB are obtained as follows according to the calculation method proposed by Fedors. For each atom or atomic group in the molecular structure, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm / mol) are obtained from the table described in "polym.Eng.Sci., 3 14(2), 147 - 154(1974)", and (4.184×ΣΔei / ΣΔvi) 0.5 is taken as the SP value (J / cm 3 ) 0.5 and so on. Specifically, the evaporation energy (Δei) and molar volume (Δvi) of the monomer units derived from the monomers constituting resin A or resin B are obtained for each monomer unit, and the product of each and the molar ratio (j) of the resin A in each monomer unit is calculated respectively. Then, the sum of the evaporation energies of each monomer unit is divided by the sum of the molar volumes to obtain the value calculated from the following formula (5). SPA or SPB = {4.184×(Σj×ΣΔei) / (Σj×ΣΔvi)} [[ID=2!]] 0.5 (5)

[0077] <Measurement method of ion count derived from silicon with mass number 28 with respect to total ion count at mass numbers 1 - 1800 in TOF - SIMS measurement> In the measurement of the toner particle surface by a time - of - flight secondary ion mass spectrometer (TOF - SIMS), the ion count derived from silicon with mass number 28 with respect to the total ion count at mass numbers 1 - 1800 is measured under the following apparatus and measurement conditions. Measuring apparatus: TOFSIMS TRIFT IV (manufactured by ULVAC - PHI, Inc.) Primary ion species: Gold ion (Au + ) Primary ion acceleration voltage: 30 keV Primary ion current value: 2 pA Analysis area: 300×300 μm 2 Please note that in the original text, there is an error in line where it should be 0.5 instead of [[ID=2!]] 0.5 . This has been corrected in the translation.Number of pixels: 256 x 256 pixels Analysis time: 3min Repetition frequency: 8.2kHz Charge neutralization: on Secondary ion polarity: Positive Secondary ion mass range (m / z): 0.5 to 1850 Analysis is performed using ULVAC-PHI's standard software (Win Cadense). The ion count derived from silicon with mass number 28 is calculated as the intensity ratio of the ion count derived from silicon with mass number 28 to the total ion count from mass numbers 1 to 1850.

[0078] <Method for measuring toner particles and toner weight average particle size (D4)> The toner particles and the weight average particle size (D4) of the toner are measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.). The measurement is performed under the following conditions. Effective number of measurement channels: 25,000 channels Total number of control motors: 50,000 Aperture: 100 μm Current: 1600μA Gain: 2 The Kd value is measured using a "10.0 μm standard particle" (manufactured by Beckman Coulter). The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4). Note that 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).

[0079] <Method for measuring the content of the structure represented by formula (4) in resin A> The content of the structure represented by formula (4) in resin A is measured using a wavelength dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. When measuring, a proportional counter (PC) is used, and when measuring heavy elements, a scintillation counter (SC) is used for detection. The measurement sample was prepared by placing 4 g of resin A or tetrahydrofuran-soluble matter obtained by the method of isolating resin A from the toner particles in a dedicated aluminum ring for pressing, flattening it, and pressing it at 20 MPa for 60 seconds using a tablet molding compression machine "BRE-32" (manufactured by Maekawa Testing Machinery Manufacturing Co., Ltd.) to form a pellet with a thickness of 2 mm and a diameter of 39 mm. In addition, binder particles [product name: Spectro Blend, components: C81.0% by mass, O2.9% by mass, H13.5% by mass, N2.6% by mass, chemical formula: C 19 H 38 SiO2 particles (hydrophobic fumed silica) [product name: AEROSIL NAX50, specific surface area: 40±10 m] per 100 parts by mass of SiO2 particles (hydrophobic fumed silica) [product name: AEROSIL NAX50, specific surface area: 40±10 m] 2 0.5 parts by mass of SiO2 particles (0.01g / g, carbon content: 0.45% to 0.85%; manufactured by Nippon Aerosil Co., Ltd.) was added and thoroughly mixed using a coffee mill. Similarly, 5.0 parts by mass and 10.0 parts by mass of the SiO2 particles were mixed with the binder particles, respectively, and these were used as samples for the calibration curve. For each sample, pellets for the calibration curve sample were prepared using a tablet press as described above, and the count rate (unit: cps) of the Si-Kα ray observed at a diffraction angle (2θ) of 109.08° when PET was used as the analyzing crystal was measured. The acceleration voltage and current of the X-ray generator were set to 24 kV and 100 mA, respectively. A linear calibration curve was obtained by plotting the obtained X-ray count rate on the vertical axis and the amount of SiO2 particles added in each calibration curve sample on the horizontal axis. Next, the resin A to be analyzed or the tetrahydrofuran-soluble fraction obtained by the method for isolating resin A from the toner particles is pelletized as described above using a tablet molding compressor, and the count rate of the Si-Kα ray is measured. Then, the content of silicon atoms in the calibration curve is determined. The content of the structure represented by formula (4) can be determined from the obtained silicon atom content and the structure of resin A obtained by the method for confirming the structure of resin A described above. [Example]

[0080] The present disclosure will be specifically described below using examples, but the present disclosure is not limited to these examples. Unless otherwise specified, the "parts" of each material in the examples and comparative examples are all based on mass.

[0081] <Production of Resin S1> Resin S1 was prepared according to the following procedure. The following materials were charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at atmospheric pressure and 200°C. When the desired molecular weight was obtained, the reaction was stopped by cooling. Bisphenol A-propylene oxide 2 mole adduct: 71.3 parts Terephthalic acid: 14.0 parts Isophthalic acid: 14.0 parts Tetrabutoxytitanate: 0.1 parts Trimellitic acid 0.9 parts Thereafter, the mixture was reacted for 2 hours under a reduced pressure of 10 mmHg to 20 mmHg to obtain a resin S1. The weight average molecular weight (Mw) of the obtained resin S1 was 19,000.

[0082] <Production of Resins S2 to S6> As shown in Table 1, resins S2 to S6 were produced in the same manner as resin S1, except that the alcohol component and acid component were changed and the reaction time was appropriately changed depending on the desired molecular weight.

[0083] [Table 1] In Table 1, BPA-PO2 mol represents a bisphenol A-propylene oxide 2 mol adduct, TPA represents terephthalic acid, IPA represents isophthalic acid, and TMA represents trimellitic acid.

[0084] <Production of Resin V1> Resin V1 was prepared according to the following procedure. 100.0 parts of propylene glycol monomethyl ether was heated while purging with nitrogen and refluxed at a liquid temperature of 120° C. or higher. A mixture of 97.0 parts of styrene and 3.0 parts of methacrylic acid as polymerizable monomers, and 0.50 parts of tert-butyl peroxybenzoate (manufactured by NOF Corporation, trade name: Perbutyl Z) as a polymerization initiator was added dropwise thereto over 3 hours. After the dropwise addition was completed, the solution was stirred for 3 hours and then distilled at atmospheric pressure while increasing the liquid temperature to 170°C. After the liquid temperature reached 170°C, the pressure was reduced to 1 hPa, and distillation was continued for 1 hour to remove the solvent, yielding a resin solid. The resin solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was filtered off to obtain resin V1. The weight average molecular weight (Mw) of the obtained resin V1 was 24,500.

[0085] <Production of Resins V2 to V6> Resins V2 to V6 were produced in the same manner as in the production of Resin V1, except that the polymerizable monomers were changed as shown in Table 2.

[0086] [Table 2]

[0087] <Production example of resin A1> Resin A1 was prepared according to the following procedure. 100.0 parts of resin S1 was dissolved in 400.00 parts of N,N-dimethylacetamide, and 1.6 parts of 3-aminopropyltrimethoxysilane as a silane compound, 3.0 parts of triethylamine, and 2.4 parts of DMT-MM [4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride] as a condensation agent were added, and the mixture was left at room temperature for 5 hours. Stirred. After the reaction was completed, the solution was dropped into methanol to reprecipitate and then filtered, yielding Resin A1. The weight average molecular weight MwA of Resin A1 was 20,000. The physical properties of the obtained Resin A1 are shown in Table 4.

[0088] <Production examples of resins A2, A4, and A7-14> Resins A2, A4, and A7 to 14 were obtained in the same manner as in the production example for Resin A1, except that the base resin, the type and amount of silane compound added, and the amount of DMT-MM added were changed as shown in Table 3. The structures and physical properties of the obtained Resins A2, A4, and A7 to 14 are shown in Table 4.

[0089] [Table 3]

[0090] <Resin A3 manufacturing example> Resin A3 was prepared according to the following procedure. 100.0 parts of Resin V2 were dissolved in 500.00 parts of chloroform, and under a nitrogen atmosphere, 2.0 parts of 3-isocyanatopropyltrimethoxysilane and 0.50 parts of titanium(IV) tetraisopropoxide were added and stirred at room temperature for 5 hours. After the reaction was completed, the solution was added dropwise to methanol, reprecipitated, and filtered to obtain Resin A3. The structure and physical properties of the resulting Resin A3 are shown in Table 4.

[0091] <Resin A5 manufacturing example> Resin A5 was obtained in the same manner as in the production example for Resin V1, except that methacrylic acid was replaced with 3-methacryloxypropyltrimethoxysilane. The structure and physical properties of the obtained Resin A5 are shown in Table 4.

[0092] <Resin A6 manufacturing example> 100.0 parts of Resin S2 were dissolved in 1000.0 parts of toluene, and under a nitrogen atmosphere, 2.5 parts of 3-methacryloxypropyltrimethoxysilane and 0.6 parts of tert-butyl peroxybenzoate (NOF Corporation, trade name: Perbutyl Z) were added and reacted at 100°C for 5 hours. The resulting solution was reprecipitated in methanol, filtered, washed, and vacuum dried to obtain Resin A6. The structure and physical properties of the resulting Resin A6 are shown in Table 4.

[0093] <Resin A15 manufacturing example> Resin A15 was obtained in the same manner as in the production example of Resin V1, except that 97.0 parts of styrene was replaced with 98.0 parts of styrene and 3.0 parts of methacrylic acid was replaced with 2.0 parts of vinyltriethoxysilane. The structure and physical properties of the obtained Resin A15 are shown in Table 4.

[0094] <Manufacturing example of resin A16> A solution of 10.0 parts of Resin A2 in 90.0 parts of toluene was mixed with 400.0 parts of pure water and stirred, the pH was adjusted to 4.0 with dilute hydrochloric acid, and the mixture was stirred at room temperature for 10.8 hours. After stopping the stirring, the mixture was transferred to a separatory funnel and the oil phase was extracted. The oil phase was concentrated and reprecipitated with methanol to obtain Resin A16. The resulting resin A16 29 Analysis by Si-NMR (solid state) measurement revealed that R 1 ~R 3 The structure and physical properties of the obtained resin A16 are shown in Table 4.

[0095] [Table 4] Production examples of resins A17 to A23 will be described later.

[0096] <Production Example of Toner Particle 1> A reaction vessel was charged with 390.0 parts of ion-exchanged water and 14.0 parts of sodium phosphate (12-hydrate) (manufactured by Rasa Kogyo Co., Ltd.), and the mixture was kept at 65 ° C for 1 hour while purging with nitrogen. Next, using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous calcium chloride solution prepared by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water was added all at once while stirring at 12,000 rpm, to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, hydrochloric acid was added to the aqueous medium, and the pH was adjusted to 6.0, to obtain aqueous medium 1. Next, the following materials were mixed: Behenyl acrylate 60.0 parts Methacrylonitrile 30.0 parts Styrene 10.0 parts Resin A1 2.0 parts Wax (Fischer-Tropsch wax, melting point: 78°C) 9.0 parts ·CIPIGMENT BLUE 15:3 6.0 copies The mixture was kept at 65° C. and uniformly dissolved and dispersed using a TK homomixer at 500 rpm to prepare a polymerizable monomer composition 1. While maintaining the temperature of the aqueous medium 1 at 70°C and the rotation speed of the stirrer at 12,000 rpm, the polymerizable monomer composition 1 was charged into the aqueous medium 1, and 8.0 parts of t-butyl peroxypivalate was added as a polymerization initiator. Granulation was continued for 10 minutes while maintaining the stirring speed at 12,000 rpm. The stirring device was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5 hours while stirring at 150 rpm and maintaining the temperature at 70°C. The temperature was then raised to 85°C and maintained at this temperature for 2 hours, and the mixture was then cooled to room temperature, thereby obtaining toner particle dispersion 1. Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.4 or less, the dispersion stabilizer was dissolved, and the mixture was filtered, washed, and dried to obtain toner particles 1. Table 5 shows the physical properties of resin B1 of toner particles 1. Table 8 shows the physical properties of toner particles 1.

[0097] <Production Examples of Toner Particles 2 to 31, 34 to 36, and Comparative Toner Particles 1 to 4> Toner particles 2 to 31, 34 to 36 and comparative toner particles 1 to 4 were produced in the same manner as in the production example of toner particle 1, except that the types and amounts of raw materials were changed as shown in Table 6. Table 8 shows the physical properties of resins B1 to B17 of toner particles 2 to 31, 34 to 36 and comparative toner particles 1 to 4.

[0098] [Table 5]

[0099] [Table 6]

[0100] In Table 6, BHA represents behenyl acrylate, OCA represents octacosyl acrylate, STA represents stearyl acrylate, LA represents lauryl acrylate, OA represents octyl acrylate, nBA represents n-butyl acrylate, MN represents methacrylonitrile, and AN represents acrylonitrile.

[0101] <Production Example of Toner Particles 32> (Manufacturing of Resin B18) Behenyl acrylate 60.0 parts Methacrylonitrile 30.0 parts Styrene 10.0 parts Toluene 100.0 parts The above materials were mixed and heated to 70°C, and then t-butyl ether was added as a polymerization initiator while stirring. 1.0 parts of peroxypivalate was added. The mixture was then maintained at 70°C and polymerized for 5 hours, then heated to 85°C and maintained there for 2 hours. After cooling, the mixture was reprecipitated in methanol, filtered, and dried to obtain Resin B18. The physical properties of the resulting Resin B18 are shown in Table 5.

[0102] Resin B18 100.0 parts ·CIPIGMENT BLUE 15:3 7.0 copies ·Resin A2 2.0 parts Paraffin wax (DSC peak temperature: 80°C) 5.0 parts The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.), and then mixed in a twin-screw mixer (PCM-30 model, manufactured by Ikegai Iron Works Co., Ltd.) at a rotation speed of 3.3 s. -1 The mixture was kneaded at a kneading temperature of 120°C. The resulting kneaded mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). The finely pulverized powder was further classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 32 having a weight average particle size of 6.1 μm. The MA / MB of the resulting toner particles 32 was 0.0200.

[0103] <Production Example of Toner Particles 33> (Production of dispersion of resin B18 resin fine particles) 60 parts of Resin B18 were added to 200 g of toluene (manufactured by Wako Pure Chemical Industries), heated to 90°C, and then stirred for 3 hours to dissolve. To the toluene solution containing Resin B18, 180 parts of ion-exchanged water containing 6 parts of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku: Neogen RK) and 3 parts of anionic surfactant (manufactured by Nippon Oil & Fats: Nonsal LN1) was added. The mixture was then thoroughly stirred at 4000 rpm using an ultra-high-speed stirring device, TK Robomix (manufactured by Primix Corporation). After approximately 1 hour of dispersion using a high-pressure impact disperser, Nanomizer (manufactured by Yoshida Kikai Kogyo), the toluene was removed using an evaporator to obtain a dispersion of Resin B18 resin microparticles.

[0104] (Production of Resin A2 Dispersion) A dispersion of Resin A2 was obtained in the same manner as in the production of the dispersion of Resin B18 fine particles, except that Resin B18 was replaced with Resin A2.

[0105] (Production of dispersion of release agent particles) Release agent (HNP-51, melting point 78°C, manufactured by Nippon Seiro) 20.0 parts Anionic surfactant (Dai-ichi Kogyo Seiyaku: Neogen RK) 1.0 part 79.0 parts ion-exchanged water The above formulation was placed in a mixing vessel equipped with a stirrer, heated to 90°C, and circulated through a Clearmix W Motion (manufactured by M Technique) where it was stirred at a shear stirring location with a rotor outer diameter of 3 cm and a clearance of 0.3 mm at a rotor rotation speed of 19,000 r / min and a screen rotation speed of 19,000 r / min, and dispersed for 60 minutes. After that, it was cooled to 40°C under cooling conditions of a rotor rotation speed of 1,000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min, to obtain a dispersion of release agent microparticles.

[0106] (Production of pigment dispersion) ·CIPigment BLUE 15:3 10.0 copies 78.0 parts ion-exchanged water 2.0 parts anionic surfactant (Dai-ichi Kogyo Seiyaku: Neogen RK) The above materials were mixed and then dispersed for 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to prepare a pigment dispersion.

[0107] 320.0 parts of dispersion of resin B18 fine particles (solid content 28%) Pigment dispersion (solid content 11%) 50.0 parts 50.0 parts of dispersion of release agent particles (20% solids) 3.2 parts of dispersion of resin A2 (28% solids) The above materials were placed in a round stainless steel flask and mixed. An aqueous solution of 8 parts magnesium sulfate dissolved in 98.0 parts ion-exchanged water was added to the flask, and the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). The mixture was then heated to 50°C in a heated water bath using a stirring blade, while adjusting the rotation speed appropriately so that the mixture was stirred. After maintaining the mixture at 50°C for 1 hour, the weight-average particle diameter of the formed aggregated particles was measured. The results confirmed that aggregated particles with a weight-average particle diameter of approximately 6.0 μm had been formed. To the resulting dispersion of aggregated particles, an aqueous solution of 40 parts of sodium ethylenediaminetetraacetate dissolved in 360 parts of ion-exchanged water was added, followed by 2,800 parts of ion-exchanged water. The mixture was heated to 80°C while continuing to stir and held in a sealed state for 2 hours to obtain fully fused particles. After filtration and solid-liquid separation, the filter cake was thoroughly washed with ion-exchanged water and dried in a vacuum dryer to obtain toner particles 33 with a weight-average particle diameter of 5.8 μm. The MA / MB ratio of the resulting toner particles 33 was 0.0100.

[0108] <Production Example of Toner Particles 37> 98.5 parts of styrene and 1.5 parts of 3-methacryloxypropyltrimethoxysilane (MPTMS) were mixed using a stirrer until a homogeneous phase was formed, yielding a monomer solution 1. Next, 50 parts of ion-exchanged water was measured out, and 50 parts of the monomer solution 1 was added thereto. Dispersion treatment was carried out using an ultrasonic homogenizer (manufactured by SONICS & MATERIAL) at 97% intensity at 25°C for 1 minute, yielding a monomer suspension 1. Toner base particle dispersion 37 was obtained in the same manner as in the production example of toner particle 1, except that resin A1 was not added, the steps from adding hydrochloric acid to drying were not performed, and the solid content concentration of the toner particle dispersion was adjusted to 20.0 mass % by adding ion-exchanged water, decanting, and filtering. 500 parts of the obtained toner base particle dispersion 37 was placed in a reaction vessel equipped with a stirrer, heated to 70°C while stirring, and purged with nitrogen for 1 hour. 2.0 parts of monomer suspension 1 and 0.1 parts of potassium persulfate (KPS) were added to the reaction vessel, and a reaction was carried out at 70°C for 3 hours to form resin A17 on the surface of the toner base particles. After cooling to room temperature, hydrochloric acid was added to adjust the pH to 1.4 or less, and stirring was continued for 1 hour. Thereafter, filtration, washing, and drying were carried out in the same manner as in the production example of toner particles 1, to obtain toner particles 37. The physical properties of the obtained toner particles 37 are shown in Table 8.

[0109] <Production Examples of Toner Particles 38 to 44> Toner particles 38 to 44 were produced in the same manner as in the production example of toner particle 37, except that the composition of resin B, the composition of the monomer solution, and the number of parts of monomer suspension added were changed as shown in Tables 7-1 and 7-2. The physical properties of the obtained toner particles 38 to 44 are shown in Table 8.

[0110] <Production Example of Toner Particle 45> Toner base particle dispersion 45 was obtained in the same manner as in the production example of toner particles 33, except that no dispersion of resin A2 was added, the processes of filtering, washing, and drying the fused particles were not performed, and the fused particles were subjected to the addition of ion-exchanged water, decantation, and filtration, and the solids concentration of the toner particle dispersion was adjusted to 20.0 mass %. Toner particles 45 were obtained in the same manner as in the production example of toner particles 37, except that toner base particle dispersion 37 was changed to toner base particle dispersion 45. The physical properties of the obtained toner particles 45 are shown in Table 8.

[0111] <Production Example of Toner Particles 46> Toner base particles 46 were obtained in the same manner as in the production example of toner particles 32, except that resin A2 was not added. 100 parts by mass of toner base particles 46 and 1.0 part by mass of Contaminon N were weighed and added to 400 parts by mass of ion-exchanged water, and dispersed using an ultrasonic disperser to obtain toner base particle dispersion 46. Thereafter, toner particles 46 were obtained in the same manner as in the production example of toner particles 37 above, except that toner base particle dispersion 37 was changed to toner base particle dispersion 46 and the monomer solution was changed as shown in Table 7-2. The physical properties of the obtained toner particles 46 are shown in Table 8.

[0112] [Table 7-1] (In Table 7-1, BHA represents behenyl acrylate, nBA represents n-butyl acrylate, and MN represents methacrylonitrile.)

[0113] [Table 7-2] (In Table 7-2, MPTMS represents 3-methacryloxypropyltrimethoxysilane, MOTMS represents 8-methacryloxyoctyltrimethoxysilane, and MN represents methacrylonitrile.)

[0114] [Table 8] *: Ion counts derived from silicon with a mass number of 28 relative to the total ion counts with mass numbers of 1 to 1800 in measurements using TOF-SIMS on the surface of toner particles

[0115] <Production Examples of Toners 1 to 46 and Comparative Toners 1 to 4> For 100.0 parts of the obtained toner particles 1 to 46 and comparative toner particles 1 to 4, a BET value of 200 m 2 / g and 0.6 parts of hydrophobic silica fine particles having a number average particle size of primary particles of 8 nm were mixed in a Henschel mixer (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.). After the above-mentioned mixing treatment, the mixture was sieved through a mesh with an opening of 150 μm to obtain toners 1 to 46 and comparative toners 1 to 4, respectively.

[0116] <Examples 1 to 46> In Examples 1 to 46, evaluations were carried out using Toners 1 to 46, respectively. The evaluation methods and results are shown below. Examples 1 to 36 were evaluated as follows as reference examples.

[0117] <Comparative Examples 1 to 4> In Comparative Examples 1 to 4, evaluation was carried out using Comparative Toners 1 to 4, respectively. The evaluation was carried out in the same manner as in Examples 1 to 46.

[0118] <Method for evaluating adhesiveness of discharged paper> The evaluation was carried out in a high temperature and high humidity environment (30°C / 80%RH) using a modified LBP712Ci (Canon) color laser printer. The modifications were as follows: The gear and software of the evaluation machine were changed to set the process speed to 350 mm / sec and the fixing temperature to 180°C. The cartridge used for evaluation was a cyan cartridge. Specifically, the product toner was removed from a commercially available cyan cartridge, the inside was cleaned with an air blower, and then 50 g of the toner to be evaluated was filled. Note that the magenta, yellow, and black cartridges were inserted into each station from which the product toner had been removed and whose remaining toner detection mechanisms had been disabled. Under the above conditions, the toner amount is 0.45 mg / cm 2 An image measuring 25.0 cm in length and 20.0 cm in width was printed in continuous double-sided mode on the media (XEROX 4200 paper (75 g / m 2 The evaluation was carried out while changing the number of sheets loaded. After printing a specified number of sheets on the output tray and leaving it for one minute, the toner stains on the bottom sheet of the stack (the first sheet printed) were evaluated according to the following criteria. The evaluation results are shown in Table 9. (Evaluation criteria) A: With a capacity of 250 sheets, there is no toner staining on the paper. B: Toner stains on paper occur when the number of sheets loaded is between 150 and 250. C: Toner stains on paper occur when the number of sheets loaded is between 50 and 150. D: Toner stains on paper when the number of sheets loaded is less than 50

[0119] <Evaluation method for low-temperature fixability> A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) with the fixing unit removed was prepared, the toner was removed from the cyan cartridge, and the toner to be evaluated was replaced. Next, a medium (GF-C081, basis weight 81.4 g / m) was 2 ) and an unfixed toner image (0.45 mg / cm) measuring 4.0 cm in length and 10.0 cm in width was created using the toner. 2 ) was formed at a position 1.0 cm from the top end in the paper feed direction. Next, the removed fixing unit was modified so that the fixing temperature and process speed could be adjusted, and the process speed was set to 230 mm / s under a normal temperature and humidity environment (23°C, 60% RH). The surface temperature of the fixing sleeve was changed from 100°C to 180°C in 5°C increments to fix the unfixed image. The minimum fixing temperature was defined as 5°C higher than the temperature at which the fixed image cold-off occurred, and the toner was ranked according to the following evaluation criteria. A rating of C or higher was considered to indicate good low-temperature fixability. The results are shown in Table 9. [Evaluation criteria] A: Minimum fixing temperature is 115°C or less B: Minimum fixing temperature is 120℃ or 125℃ C: Minimum fixing temperature is 130℃ or 135℃ D: Minimum fixing temperature is 140°C or higher

[0120] <Method for evaluating heat resistance storage stability> 5g of each toner was placed in a 50cc resin cup and left to stand for 72 hours at a temperature of 50°C / humidity of 10%RH and at a temperature of 55°C / humidity of 10%RH. In this disclosure, a rating of C or higher was considered to indicate good heat-resistant storage stability. The results are shown in Table 9. [Evaluation criteria] A: No clumps formed B: Slight clumps formed, crumbles when lightly pressed with fingers C: Agglomerates form, but do not crumble when lightly pressed with fingers D: Completely aggregated

[0121] <Image quality evaluation in low temperature and low humidity environments> As an index for evaluating image quality, fogging in non-image areas was evaluated. The fogging was evaluated in a low-temperature, low-humidity environment (15°C / 10%RH). 2) was used. The same evaluation machine and toner cartridge were used as in the evaluation of paper discharge adhesion. A solid white image was output, and the worst reflection density of the white background was defined as Ds, the average reflection density of the transfer material before image formation was defined as Dr (%), and [Dr - Ds (%)] was defined as the fog value. The reflection density of the white background was measured using a reflection densitometer (Reflectometer Model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.) and an amber light filter. The smaller the value, the better the evaluation. The evaluation criteria are as follows. The evaluation results are shown in Table 9. (Evaluation criteria) A: Less than 0.50% B: 0.50% or more and less than 1.50% C: 1.50% or more and less than 3.00% D: 3.00% or more

[0122] [Table 9]

Claims

1. Toner base particles containing resin B, and Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2): A toner characterized by: 【Chemical 1】 [In formula (1), P １ represents a polymer moiety, and R １ ~R ３ each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R １ ~R ３ at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L １ represents an alkylene group having 8 or less carbon atoms, *-O-**, *-OR ５ -**, *-NH-**, *-NH-R ６ -**, * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R ５ , R ６ are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; When m is 2 or more, a plurality of L １ , multiple R １ , multiple R ２ and multiple R ３ may be the same or different. 【Chemistry 2】 [In formula (2), R ４ represents a hydrogen atom or a methyl group, and n represents an integer of 17 to 29.

2. Toner base particles containing resin B, and Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3): A toner characterized by: 【Chemistry 3】 [In formula (1), P １ represents a polymer moiety, and R １ ~R ３ each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R １ ~R ３ at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L １ represents an alkylene group having 8 or less carbon atoms, *-O-**, *-OR ５ -**, *-NH-**, *-NH-R ６ -**, * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R ５ , R ６ are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; When m is 2 or more, a plurality of L １ , multiple R １ , multiple R ２ and multiple R ３ may be the same or different. 【Chemistry 4】 [In formula (2), R ４ represents a hydrogen atom or a methyl group, and n represents an integer of 11 to 35. 【Chemistry 5】 [In formula (3), R ７ represents a hydrogen atom or a methyl group.

3. Toner base particles containing resin B, and Resin A formed on the surface of the toner base particles 1. A toner having toner particles having The resin A has a structure represented by the following formula (1): The resin B has a monomer unit represented by the following formula (2): When the content of the resin A in the toner particles is MA (mass%) and the content of the resin B in the toner particles is MB (mass%), MA / MB satisfies the following relationship: 0.0050≦[MA / MB]≦0.2000. A toner characterized by: 【Chemistry 6】 [In formula (1), P １ represents a polymer moiety, and R １ ~R ３ each independently represents a hydrogen atom, an alkyl group having one or more carbon atoms, an alkoxy group having one or more carbon atoms, or a hydroxy group; R １ ~R ３ at least one of represents an alkoxy group or a hydroxy group having one or more carbon atoms, and m represents a positive integer; L １ represents an alkylene group having 8 or less carbon atoms, *-O-**, *-OR ５ -**, *-NH-**, *-NH-R ６ -**, * represents the bond to the carbonyl group in formula (1), ** represents the bond to the silicon atom, and R ５ , R ６ are each an alkylene group having 8 or less carbon atoms, each of which may have a hydroxyl group as a substituent; When m is 2 or more, a plurality of L １ , multiple R １ , multiple R ２ and multiple R ３ may be the same or different. 【Chemistry 7】 [In formula (2), R ４ represents a hydrogen atom or a methyl group, and n represents an integer of 11 to 35.

4. Said L １ However, *-NHR ６ The toner according to any one of claims 1 to 3, wherein the toner is represented by -**.

5. Said L １ However, *-OR ５ The toner according to any one of claims 1 to 3, wherein the toner is represented by -**.

6. 6. The toner according to claim 1, wherein the content of the structure represented by the following formula (4) in the resin A is 0.5% by mass or more and 10.0% by mass or less: 【Chemistry 8】 [In formula (4), R １ ~R ３ is R in formula (1) １ ~R ３ and L １ is L in formula (1). １ is the same as above.]

7. The SP value of the resin A measured by the Fedors method is SPA [(J / m ３ ) ０．５ ], and the SP value of the resin B measured by the Fedors method is defined as SPB [(J / m ３ ) ０．５ ], |SPA-SPB|≦2.00 [(J / m ３ ) ０．５ 7. The toner according to claim 1, wherein:

8. 8. The toner according to claim 1, wherein the weight average molecular weight MwA of the resin A is 8,000 or more and 50,000 or less.

9. 9. The toner according to claim 1, wherein the weight average molecular weight MwB of the resin B is 15,000 or more and 250,000 or less.

10. 10. The toner according to claim 1, wherein the resin A further has a monomer unit represented by the following formula (3): 【Chemistry 9】 [In formula (3), R ７ represents a hydrogen atom or a methyl group.

11. The P １ The toner according to any one of claims 1 to 10, wherein represents a polyester resin moiety.

12. The P １ The toner according to any one of claims 1 to 10, wherein represents a vinyl resin moiety.

13. The toner according to any one of claims 1 to 12, wherein the formula (1) is at least one selected from the group consisting of structures represented by the following formulas (7) to (12): 【Chemistry 10】 (R in formulas (7) to (12) １ ~R ３ , R ５ ~R ６ is R in formula (1) １ ~R ３ , R ５ ~R ６ and R ７ represents a hydrogen atom or a methyl group, and R in formulas (9) and (10) ９ , R １０ represents an alkylene group having 1 to 6 carbon atoms, and P in formulas (11) and (12) ２ represents the main chain skeleton of the polyester resin.) 14. The toner according to claim 1, wherein the content of the monomer unit represented by formula (2) in resin B is 5.0% by mass or more and 95.0% by mass or less.

15. The toner according to claim 1, wherein the content of said resin A in said toner particles is 0.40% by mass or more and 4.0% by mass or less.

16. The toner according to claim 1, wherein the content of said resin B in said toner particles is 40.0% by mass or more and 90.0% by mass or less.

17. A method for producing the toner according to any one of claims 1 to 16, comprising the steps of: The method comprises: a step of dispersing the toner base particles containing the resin B in an aqueous medium to obtain a toner slurry; a step of adding a monomer composition containing a monomer represented by the following formula (6) and a radical polymerization initiator to the obtained toner slurry to form the resin A on the surfaces of the toner base particles; The toner manufacturing method according to the present invention comprises the steps of: 【Chemistry 11】 [In formula (6), R ８ represents a hydrogen atom or a methyl group.

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