Toner and Method for Producing Toner

Abstract

To provide a toner that is excellent in low temperature fixability and high stability, and with which color unevenness is less likely to occur even when a high printing ratio image is printed.SOLUTION: A toner has a toner particle having a surface layer containing an organic silicon polymer. The toner particle contains binder resin, hydrocarbon wax, and an ester compound represented by a specific formula. The organic silicon polymer has a partial structure represented by a specific formula. In measurement of 29Si-NMR of a tetrahydrofuran insoluble in the toner particle, when [SX2] is the ratio of the peak area of a partial structure represented by the following formula (X2) to the total peak area of the organic silicon polymer, and [SX1] is the ratio of the peak area of a partial structure represented by the following formula (X1), the [SX2] and the [SX1] satisfy 30%≤[SX2]+[SX1]≤90%.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and a toner jet method, and a method for manufacturing the same.

Background Art

[0002] In recent years, there has been a demand for high speed and low power consumption in printers and copiers, and the development of a toner with excellent low-temperature fixability has been required. On the other hand, high stability without image quality degradation even in multiple copies and prints is also a performance required of the toner. In contrast, the present inventors have proposed a toner in which toner particles containing a specific ester compound and a release agent are coated with an organosilicon polymer as in Patent Document 1.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] Although the toner described in Patent Document 1 has excellent low-temperature fixability and high stability against durability, it has been found that color unevenness may occur in one image when printing a high print density image such as solid black. The present invention provides a toner in view of the above background art. That is, the present invention provides a toner that is excellent in low-temperature fixability and high stability, and is less likely to cause color unevenness even when printing a high print density image.

Means for Solving the Problems

[0005] The present invention is a toner having toner particles having a surface layer containing an organosilicon polymer, The toner particles contain a binder resin, a hydrocarbon wax, and an ester compound represented by the following formula (1) or (2).

[0006] [Chemical formula] ( front In formula (1) and front formula (2), R 1 and R 4 each represent an alkylene group having 1 to 6 carbon atoms, and R 2 , R 3 , R 5 and R 6 each independently represent a linear alkyl group having 11 to 25 carbon atoms.) The organosilicon polymer has at least one partial structure represented by the following formula (X2) and a partial structure represented by the following formula (X1).

[0007] [Chemical formula] ( front In formula (X2) and front formula (X1), R 7 ~R 11 each independently represent an organic group bonded to a silicon atom, a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group.) A substructural part other than the substructural part represented by the formula (X2) and the substructural part represented by the formula (X1) of the organosilicon polymer is at least one substructural part of a substructural part represented by the formula (X3-A) described later and a substructural part represented by the formula (X4-A) described later. In the measurement of Si-NMR of the tetrahydrofuran-insoluble content of the toner particles, when the ratio of the peak area of the partial structure represented by formula (X2) to the total peak area of the organosilicon polymer is [SX2], and 29 the ratio of the peak area of the partial structure represented by formula (X1) is [SX1], the toner is characterized in that [SX2] and [SX1] satisfy front 30% ≦ [SX2] + [SX1] ≦ 90% front Further, the present invention relates to The organosilicon polymer in the toner is a polymer of a composition containing at least one monomer represented by the formula (A) described later and at least one monomer represented by the formula (B) described later, and at least one monomer represented by the formula (C) described later and at least one monomer represented by the formula (D) described later. a method for manufacturing a toner having the following configuration, wherein the manufacturing method​​​ (i) A step of preparing an aqueous medium in which particles containing a binder resin, a hydrocarbon wax, and the ester compound are dispersed. (ii) A step of mixing at least one monomer represented by the formula (A) and at least one monomer represented by the formula (B), and at least one monomer represented by the formula (C) and at least one monomer represented by the formula (D) to prepare a composition containing an organosilicon monomer. (iii) A step of mixing the composition containing the organosilicon monomer with the aqueous medium, and (iv) A step of polymerizing the composition containing the organosilicon monomer. The present invention relates to a method for producing a toner, which comprises the above steps in this order. [Effect of the Invention]

[0008] According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and high stability, and in which color unevenness hardly occurs even when a high-printing-rate image is printed. [Embodiments for Carrying Out the Invention]

[0009] In the present invention, the description of "○○ or more and ×× or less" or "○○ to ××" representing a numerical range means a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified.

[0010] In the present invention, "(meth)acryl" means "acryl" and / or "methacryl".

[0011] Hereinafter, the toner of the present invention will be described in more detail, but the present invention is not limited to these descriptions.

[0012] The present inventors have intensively studied to solve the above-mentioned problems of the prior art. As a result, it has been found that in a toner having toner particles having a surface layer containing an organosilicon polymer and containing a binder resin and a hydrocarbon wax, the above problems can be solved by controlling the partial structure of the organosilicon polymer.

[0013] That is, the toner of the present invention is a toner having toner particles with a surface layer containing an organosilicon polymer, wherein the toner particles contain a binder resin, a hydrocarbon wax, and an ester compound represented by the following formula (1) or (2).

[0014]

Chemical formula

[0015] Furthermore, the organosilicon polymer has at least one partial structure represented by the following formula (X2) and a partial structure represented by the following formula (X1),

[0016]

Chemical formula

[0017] When, in the measurement of Si-NMR of the tetrahydrofuran-insoluble matter of the toner particles, the ratio of the peak area of the partial structure represented by the formula (X2) to the total peak area of the organosilicon polymer is [SX2], and the ratio of the peak area of the partial structure represented by the formula (X1) is [SX1], the [SX2] and the [SX1] satisfy 29 30%≦[SX2]+[SX1]≦90% 30%≦[SX2]+[SX1]≦90% This is a characteristic feature.

[0018] The inventors of the present invention presume that color unevenness when printing a high printing rate image is caused by the non-uniform presence of crystalline materials such as plasticizers and release agents on the surface of the fixed image. The plasticizer melts due to heat during fixing and exhibits the effect of improving low-temperature fixability by dissolving in the binder resin. On the other hand, the release agent melts due to heat during fixing, and part or all of it oozes out between the fixing member such as a fixing roller and the toner image to exhibit releasability. The image after passing through the fixing member is gradually cooled toward room temperature, and during this process, the plasticizer and the release agent recrystallize from the molten state again. It is considered that the behavior of the release agent and the plasticizer in this cooling process greatly contributes to the color unevenness of the fixed image.

[0019] As described above, since the release agent immediately after passing through the fixing member is in a state of oozing out on the image surface, it can move relatively freely on the image, and there is a tendency for the release agents to aggregate. Since crystallization occurs after aggregation, the state of existence on the image surface tends to be non-uniform.

[0020] On the other hand, the plasticizer immediately after passing through the fixing member is in a state of being dissolved in the binder resin, which is a constituent component of the image, and in the cooling process, most of it is considered to crystallize uniformly within the binder resin. However, the plasticizer present in the vicinity of the release agent crystallizes using the release agent as a crystal nucleus and is thus pulled out onto the image surface, resulting in an even greater increase in the non-uniformity of the state of existence. It is presumed that the non-uniform presence of crystals on the image surface causes different light scattering for each location on the image, which manifests as color unevenness.

[0021] In contrast, in this case, it has been found that the above problems can be solved by providing a surface layer containing an organosilicon polymer with a controlled partial structure. Specifically, in the measurement of 29Si-NMR of the tetrahydrofuran-insoluble content of the toner particles, when the ratio of the peak area of the partial structure represented by formula (X2) to the total peak area of the organosilicon polymer is [SX2], and the ratio of the peak area of the partial structure represented by formula (X1) is [SX1], 30% ≦ [SX2] + [SX1] ≦ 90% It has been found that the above problems can be solved by controlling so that this condition is satisfied.

[0022] In the present invention, as the reason for obtaining such an effect, the present inventors consider as follows.

[0023] [SX2] + [SX1] is the ratio of the X2 structure and the X1 structure in the entire organosilicon polymer. The X2 structure represents a partial structure in which two adjacent silicon atoms are siloxane-bonded, and the X1 structure represents a partial structure in which only one adjacent silicon atom is siloxane-bonded. A large value of [SX2] + [SX1] indicates that the degree of crosslinking of the organosilicon polymer is small, and conversely, a small value of [SX2] + [SX1] indicates that the degree of crosslinking of the organosilicon polymer is large. As a result of the study by the present inventors, it has been found that by increasing the value of [SX2] + [SX1], the compatibility of the crystalline material with the organosilicon polymer can be improved. When such an organosilicon polymer is disposed on the toner particle surface layer, in the image immediately after passing through the above-described fixing member, it is considered that the crystalline material melted in the organosilicon polymer is present in a compatible state. The fact that they are present in a compatible state means that their existence positions are fixed in the organosilicon polymer, and aggregation of the crystalline material from immediately after passing through the fixing member until crystallization is greatly suppressed. As a result, crystallization during cooling occurs finely and uniformly on the image surface, light scattering becomes uniform over the entire region on the image, and color unevenness is suppressed. It is considered that the object of the present invention, that is, excellent low-temperature fixability, high stability, and difficulty in generating color unevenness, is achieved by such a mechanism.

[0024] When [SX2] + [SX1] exceeds 90%, although there is a great effect in suppressing color unevenness, the degree of crosslinking of the organosilicon polymer is significantly lost, the rigidity becomes insufficient, and there is a concern about durability.

[0025] Conversely, if [SX2]+[SX1] is less than 30%, the crystalline material will not be sufficiently compatible with the organosilicon polymer shell, and the effect of suppressing color unevenness will not be achieved. From the viewpoint of suppressing color unevenness, it is more preferable for [SX2]+[SX1] to be 60% or more.

[0026] In addition, among the partial structure represented by (X2) and the partial structure represented by (X1), the total proportion of the partial structure represented by the following formula (X2-A) and the partial structure represented by the following formula (X1-A) is preferably 80% or more.

[0027] [ka] (In the above formula (X2-A) and the above formula (X1-A), R 12 ~R 16 each independently represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom.

[0028] This means that in 80% or more of the X2 and X1 structures, the functional groups not involved in the siloxane bond are partial structures of aliphatic hydrocarbons or aryl groups with carbon numbers of 1 to 6. This brings the polarity of the organosilicon polymer closer to that of the crystalline material, making the organosilicon polymer and the crystalline material more compatible with each other and achieving a more pronounced effect in suppressing color unevenness.

[0029] The total proportion of the partial structures represented by [SX2], [SX1], and (X2), and the partial structure represented by (X1), including the partial structures represented by (X2-A) and (X1-A), can be controlled by the type and amount of monomer used to form the organosilicon polymer, as well as the reaction temperature, reaction time, reaction solvent, and pH of the hydrolysis, addition polymerization, and condensation polymerization during the formation of the organosilicon polymer.

[0030] In addition, from the viewpoint of environmental stability, it is preferable that the partial structure represented by (X2) and the partial structure other than the partial structure represented by (X1) are the partial structure represented by the following formula (X3-A) and the partial structure represented by the following formula (X4-A).

[0031] [Chemical formula] (In the above formula (X3-A), R 17 represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom.)

[0032] Among them, the organosilicon polymer is preferably a polymer of a composition containing at least one monomer selected from the monomer represented by the following formula (A) and the monomer represented by the following formula (B).

[0033] [Chemical formula] (In the above formula (A) and the above formula (B), R 18 , R 19 , R 20 , R 22 , R 23 each independently represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom. R 21 , R 24 , R 25 each independently represents a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group.)

[0034] The monomer represented by formula (A) is a so-called bifunctional silane compound.

[0035] Specific examples include dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldichlorosilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, etc.

[0036] The monomer represented by formula (B) is a so-called monofunctional silane compound.

[0037] Specific examples include trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, dimethylphenylchlorosilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, tert-butyldimethylchlorosilane, tert-butyldimethylmethoxysilane, tert-butyldimethylethoxysilane, tert-butyldiphenylchlorosilane, tert-butyldiphenylmethoxysilane, tert-butyldiphenylethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, etc.

[0038] Furthermore, it is preferable that the organosilicon polymer is a polymer of a composition containing at least one monomer of the monomer represented by the formula (A) and the monomer represented by the formula (B), and at least one monomer of the monomer represented by the following formula (C) and the monomer represented by the following formula (D).

[0039]

Chemical formula

[0040] The monomer represented by the formula (C) is a so-called trifunctional silane compound.

[0041] Specific examples include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, Examples include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane and the like.

[0042] It is a monomer represented by formula (D), that is, a so-called tetrafunctional silane compound. Specific examples include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, and the like.

[0043] In the present invention, an organosilicon compound other than the monomers represented by formulas (A) to (D) may be used in combination to such an extent that the effects of the invention are not impaired.

[0044] Specific examples include trifunctional vinyl silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, hexamethyldisilane, tetraisocyanatosilane, methyltriisocyanatosilane; vinyltriisocyanatosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylmethoxyethoxyhydroxysilane, vinyldiethoxyhydroxysilane.

[0045] Trifunctional allylsilanes such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, allyltrimethoxysilane, and allyltris(hydroxy)silane.

[0046] t-Butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chloro(decyl)dimethylsilane, methoxy(decyl)dimethylsilane, ethoxy(decyl)dimethylsilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, chloromethyl(dichloro)methylsilane, chloromethyl(dimethoxy)methylsilane, chloromethyl(diethoxy)methylsilane, di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, dichloro(methyl)-n-octylsilane, dimethoxy(methyl)-n-octylsilane, diethoxy(methyl)-n-octylsilane.

[0047] Furthermore, monomers represented by formulas (A) to (D) and organotitanium compounds or organoaluminum compounds may be used in combination with the above organosilicon compounds to the extent that the effects of the invention are not impaired.

[0048] Each component constituting the toner and the method for producing the toner will be described below.

[0049] <Binder resin> The toner particles contain a binder resin. The content of the binder resin is preferably 50% by mass or more based on the total amount of the resin components in the toner particles.

[0050] The binder resin is not particularly limited, and examples thereof include styrene acrylic resins, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, mixed resins and composite resins thereof. Styrene acrylic resins and polyester resins are preferred in terms of low cost, easy availability and excellent low-temperature fixability. More preferably, it contains a styrene acrylic resin in terms of excellent development durability.

[0051] The polyester resin is obtained by selecting suitable ones from polycarboxylic acids, polyols, hydroxycarboxylic acids, etc. and combining them, and synthesizing them using a conventionally known method such as a transesterification method or a polycondensation method.

[0052] The polycarboxylic acid is a compound containing two or more carboxy groups in one molecule. Among these, dicarboxylic acids are compounds containing two carboxy groups in one molecule and are preferably used.

[0053] For example, oxalic acid, succinic acid, glutaric 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, suberic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic 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, cyclohexanedicarboxylic acid, etc. can be mentioned.

[0054] In addition, examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, isododecylsuccinic acid, isododecenylsuccinic acid, n-octylsuccinic acid, n-octenylsuccinic acid, and the like. These may be used alone or in combination of two or more.

[0055] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among these, a diol is a compound containing two hydroxyl groups in one molecule and is preferably used.

[0056] Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols, and the like.

[0057] Among these, preferred ones are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Particularly preferred ones are alkylene oxide adducts of bisphenols and the combined use of these with alkylene glycols having 2 to 12 carbon atoms.

[0058] Examples of the alcohol having trivalent or higher valency include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolemelamine, tetramethylolbenzoguanamine, tetraethylolebenzoguanamine, sorbitol, trisphenol PA, phenol novolak, cresol novolak, and alkylene oxide adducts of the above-mentioned polyphenols having trivalent or higher valency. These may be used alone or in combination of two or more.

[0059] Examples of the styrene acrylic resin include a homopolymer composed of the following polymerizable monomers, a copolymer obtained by combining two or more of these, and further a mixture thereof.

[0060] Styrene-based monomers 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; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, (meth)acrylic monomers such as maleic acid; Vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene and butadiene.

[0061] Also, from the viewpoint of improving the compatibility with the plasticizer, it is preferable to contain lauryl acrylate, stearyl acrylate and behenyl acrylate in a proportion of 1% by mass or more and 10% by mass or less of the monomers constituting the styrene acrylic resin used as the binder resin.

[0062] Styrene acrylic resin can use a polyfunctional polymerizable monomer as needed. Examples of the polyfunctional polymerizable monomer include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2’ - bis(4 - ((meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether, etc.

[0063] In addition, in order to control the degree of polymerization, it is also possible to further add known chain transfer agents and polymerization inhibitors.

[0064] Examples of the polymerization initiator for obtaining styrene acrylic resin include organic peroxide - based initiators and azo - based polymerization initiators.

[0065] Examples of the organic peroxide - based initiators include benzoyl peroxide, lauroyl peroxide, di - α - cumyl peroxide, 2,5 - dimethyl - 2,5 - bis(benzoylperoxy)hexane, bis(4 - t - butylcyclohexyl) peroxydicarbonate, 1,1 - bis(t - butylperoxy)cyclododecane, t - butyl peroxymaleic acid, bis(t - butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert - butyl peroxy - 2 - ethylhexanoate, diisopropyl peroxydicarbonate, cumene hydroperoxide, 2,4 - dichlorobenzoyl peroxide, and tert - butyl - peroxypivalate, etc.

[0066] Examples of the azo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile, 2,2'-azobis-(methyl isobutyrate), and the like.

[0067] In addition, as the polymerization initiator, a redox initiator obtained by combining an oxidizing substance and a reducing substance can also be used.

[0068] Examples of the oxidizing substances include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salts, potassium salts, and ammonium salts), and oxidizing metal salts of tetravalent cerium salts.

[0069] Examples of the reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having about 1 to 6 carbon atoms such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), ascorbic acid or its salts, and lower aldehydes (having 1 to 6 carbon atoms).

[0070] The polymerization initiator is selected with reference to the 10-hour half-life temperature and is used alone or in combination. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally, 0.5 parts by mass or more and 20.0 parts by mass or less are added based on 100.0 parts by mass of the polymerizable monomer.

[0071] <Release agent> The toner of the present invention contains, as a release agent, hydrocarbon waxes typified by paraffin wax, polyolefin wax, and Fischer-Tropsch wax. Since the release agent is a hydrocarbon wax, the compatibility between the release agent and the organic silicon polymer is improved, and the effects of the present invention are exhibited.

[0072] In addition to the hydrocarbon wax described above, known waxes can be used in combination as a release agent in the toner of the present invention.

[0073] Specifically, paraffin wax, microcrystalline wax, petroleum waxes typified by petrolatum and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives by the Fischer-Tropsch method, polyolefin waxes typified by polyethylene and their derivatives, carnauba wax, natural waxes typified by candelilla wax and their derivatives are mentioned. The derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products.

[0074] Also, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or their acid amides, esters, ketones; hydrogenated castor oil and its derivatives, plant waxes, and animal waxes are mentioned. These can be used alone or in combination.

[0075] In addition, antioxidants may be added to these waxes as long as the effects of the present invention of the toner are not affected.

[0076] Also, the content Chc of the release agent in the toner is preferably 1.0 mass% or more and 30.0 mass% or less.

[0077] The melting point of the release agent is preferably 30°C or higher and 120°C or lower, more preferably 60°C or higher and 100°C or lower. By using a release agent having the above thermal characteristics, the release effect is efficiently exhibited and a wider fixing area is ensured.

[0078] <Plasticizer> In the toner of the present invention, a crystalline plasticizer is used to improve the sharp melting property. Specifically, it contains an ester compound represented by the above formula (1) or (2) as a plasticizer.

[0079] The ester compound represented by formula (1) is an ester compound of a dihydric diol and an aliphatic carboxylic acid. Specifically, examples include ethylene glycol dipalmitate, ethylene glycol distearate, ethylene glycol dibehenate, butanediol dipalmitate, butanediol distearate, butanediol dibehenate, hexanediol dilaurate, hexanediol dipalmitate, hexanediol distearate, hexanediol dibehenate, and the like.

[0080] The ester compound represented by formula (2) is an ester compound of a dicarboxylic acid and an aliphatic alcohol. Specifically, examples include dipentacosanyl succinate, dibehenyl adipate, distearyl sebacate, dibehenyl sebacate, and the like.

[0081] The content Ces of the ester compound in the toner is preferably 5% by mass or more and 30% by mass or less, and more preferably 8% by mass or more and 20% by mass or less.

[0082] Also, it is preferable to control the contents of the ester compound and the mold release agent so that the ratio Ces / Chc of the content of the ester compound to the content of the mold release agent is 10 or less.

[0083] In the toner of the present invention, a known plasticizer can be used in combination with the ester compound represented by the above formula (1) or (2) as long as the effects of the invention are not impaired.

[0084] Specifically, esters of monohydric alcohols and aliphatic carboxylic acids such as behenyl behenate, stearyl stearate, and palmitil palmitate, or esters of monohydric carboxylic acids and aliphatic alcohols; esters of trihydric alcohols and aliphatic carboxylic acids such as glyceryl tribehenate, or esters of trihydric carboxylic acids and aliphatic alcohols; esters of tetrahydric alcohols and aliphatic carboxylic acids such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, or esters of tetrahydric carboxylic acids and aliphatic alcohols; esters of hexahydric alcohols and aliphatic carboxylic acids such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of hexahydric carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols and aliphatic carboxylic acids such as polyglyceryl behenate, or esters of polyhydric carboxylic acids and aliphatic alcohols; natural ester waxes such as carnauba wax and rice wax can be mentioned.

[0085] <Colorant> The toner particles may contain a colorant. As the colorant, known pigments and dyes can be used. From the viewpoint of excellent weather resistance, a pigment is preferable as the colorant.

[0086] Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds.

[0087] Specifically, the following can be mentioned. C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0088] Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.

[0089] Specifically, the following can be mentioned. C.I. 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, 184, 185, 202, 206, 220, 221 and 254, and C.I. Pigment Violet 19.

[0090] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

[0091] Specifically, the following can be mentioned. C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194.

[0092] Examples of black colorants include carbon black and those toned to black using the above yellow colorants, magenta colorants, and cyan colorants.

[0093] These colorants can be used alone, as a mixture, or even in a solid solution state.

[0094] It is preferable to use the colorant in an amount of 1.0 part by mass or more and 20.0 parts by mass or less based on 100.0 parts by mass of the binder resin.

[0095] <Charge control agent, and charge control resin> The toner particles may contain a charge control agent or a charge control resin.

[0096] As the charge control agent, known ones can be used, and in particular, a charge control agent with a fast triboelectric charging speed and capable of stably maintaining a certain triboelectric charge amount is preferable. Furthermore, when the toner particles are produced by the suspension polymerization method, a charge control agent with low polymerization inhibitory properties and substantially no solubilized product in the aqueous medium is particularly preferable.

[0097] As charge control agents, there are those that control the toner to be negatively charged and those that control it to be positively charged.

[0098] Examples of those that control the toner to be negatively charged include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acid 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 naphthenic acid-based compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge control resins.

[0099] Examples of charge control agents that control the toner to be positively charged include the following.

[0100] Guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthalenesulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, and their lake pigments; triphenylmethane dyes and their lake pigments (as lake-forming agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide); metal salts of higher fatty acids; charge control resins.

[0101] Among these charge control agents, metal-containing salicylic acid-based compounds are preferred, and those in which the metal is aluminum or zirconium are particularly preferred.

[0102] Examples of the charge control resin include polymers or copolymers having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group. As the polymer having a sulfonic acid group, a sulfonate group, or a sulfonic acid ester group, a polymer containing a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more is preferable, and a polymer containing 5% by mass or more is more preferable.

[0103] The charge control resin preferably has a glass transition temperature (Tg) of 35°C or higher and 90°C or lower, a peak molecular weight (Mp) of 10,000 or higher and 30,000 or lower, and a weight average molecular weight (Mw) of 25,000 or higher and 50,000 or lower. When this is used, preferable triboelectric charging characteristics can be imparted without affecting the thermal characteristics required for toner particles. Furthermore, since the charge control resin contains a sulfonic acid group, for example, the dispersibility of the charge control resin itself and the dispersibility of a colorant in a polymerizable monomer composition are improved, and the coloring power, transparency, and triboelectric charging characteristics can be further improved.

[0104] These charge control agents or charge control resins may be added alone or in combination of two or more.

[0105] The addition amount of the charge control agent or charge control resin is preferably 0.01 part by mass or more and 20.0 parts by mass or less, more preferably 0.5 part by mass or more and 10.0 parts by mass or less, based on 100.0 parts by mass of the binder resin.

[0106] <Organic silicon polymer> The toner particles used in the toner of the present invention are toner particles having a surface layer containing an organic silicon polymer. The partial structure of the organic silicon polymer of the present invention and the monomers used are as described above.

[0107] As a typical production example of the organic silicon polymer, a production method called the sol-gel method can be mentioned.

[0108] Generally, in the sol-gel reaction, it is known that the bonding state of the siloxane bonds formed depends on the acidity of the reaction medium. Specifically, when the medium is acidic, a hydrogen ion is electrophilicly added to the oxygen of one reaction group (for example, an alkoxy group; -OR group). Next, the oxygen atom in the water molecule coordinates to the silicon atom and becomes a hydrosilyl group through a substitution reaction. When there is sufficient water, H + attacks one oxygen of the reaction group (for example, an alkoxy group; -OR group) by itself, so when the content of H + in the medium is low, the substitution reaction to the hydroxy group becomes slow. Therefore, before all the reaction groups attached to the silane are hydrolyzed, a polycondensation reaction occurs, and it is relatively easy to generate one-dimensional linear polymers and two-dimensional polymers.

[0109] On the other hand, when the medium is alkaline, a hydroxide ion is added to the silicon and passes through a pentacoordinate intermediate. Therefore, all reaction groups (for example, alkoxy groups; -OR groups) are easily desorbed and are easily substituted with silanol groups. In particular, when a silicon compound having three or more reaction groups in the same silane is used, hydrolysis and polycondensation occur three-dimensionally, and an organosilicon polymer with many three-dimensional cross-linkages is formed. Also, the reaction ends in a short time.

[0110] In addition, since the sol-gel method starts from a solution and forms a material by gelling the solution, various fine structures and shapes can be created. In particular, when toner particles are produced in an aqueous medium, they are likely to be present on the surface of the toner particles due to the hydrophilicity of hydrophilic groups such as the silanol groups of the organosilicon compound.

[0111] Therefore, to form an organosilicon polymer, it is preferable to proceed with the sol-gel reaction in an alkaline state of the reaction medium. When producing in an aqueous medium, specifically, it is preferable to proceed with the reaction at pH 8.0 or higher, a reaction temperature of 50 °C or higher, and a reaction time of 5 hours or longer. By this, an organosilicon polymer with higher strength and excellent durability can be formed.

[0112] <Method for manufacturing toner> The method for manufacturing toner particles is not particularly limited, and known methods can be adopted. Preferably, it is the suspension polymerization method. That is, the toner particles are preferably suspension polymerization toner particles.

[0113] The suspension polymerization method is a method of forming particles of a polymerizable monomer composition containing a polymerizable monomer for forming a binder resin, a release agent, and, if necessary, a plasticizer, a colorant, an organosilicon compound, and other additives in an aqueous medium, and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles.

[0114] Here, as a first method for forming the surface layer of the organosilicon polymer, a method of adding an organosilicon compound to the above polymerizable monomer composition can be mentioned. When an organosilicon compound is added, since it is polymerized in a state where the organosilicon compound is precipitated near the surface of the toner particles, a surface layer containing the organosilicon polymer can be formed on the toner particles. Further, when this manufacturing method is used, it is easy to precipitate the organosilicon polymer uniformly.

[0115] As a second method, it is a method of forming the surface layer of the organosilicon polymer in an aqueous medium after obtaining the mother body of the toner particles. The mother body of the toner particles is preferably manufactured using a melt kneading and pulverizing method, an emulsion aggregation method, a dissolution suspension method, or the like. From the viewpoint of the uniformity of the surface layer containing the organosilicon polymer formed on the surface of the toner particles, the suspension polymerization method is preferable. The polymerizable monomer in the suspension polymerization method can be the polymerizable monomer used for the styrene acrylic resin described in the above binder resin section.

[0116] Regarding the formation of the surface layer of the organosilicon polymer, the following method is preferable in the present invention. First, mother body particles of toner containing a binder resin and a release agent are manufactured and dispersed in an aqueous medium to obtain a mother body particle dispersion liquid. The concentration at this time is preferably dispersed at a concentration such that the solid content of the mother body particles is 10% by mass to 40% by mass with respect to the total amount of the mother body particle dispersion liquid. And it is preferable to adjust the temperature of the mother body particle dispersion liquid to 35°C or higher.

[0117] Also, it is preferable to adjust the pH of the mother particle dispersion to a pH at which the condensation of the organosilicon compound hardly proceeds. Since the pH at which the condensation of the organosilicon polymer hardly proceeds varies depending on the substance, it is preferably within ±0.5 around the pH at which the reaction hardly proceeds most.

[0118] On the other hand, it is preferable to use an organosilicon compound that has been subjected to a hydrolysis treatment. For example, it is preferable to hydrolyze it in a separate container as a pretreatment of the organosilicon compound. When the amount of the organosilicon compound is 100 parts by mass, the charged concentration of hydrolysis is preferably 40 to 500 parts by mass of water from which ionic components such as ion-exchanged water and RO water have been removed, more preferably 100 to 400 parts by mass of water. As the conditions for hydrolysis, preferably the pH is 2 to 7, the temperature is 15°C to 80°C, and the time is 30 minutes to 600 minutes.

[0119] By mixing the obtained hydrolysis solution and the mother particle dispersion and adjusting the pH suitable for condensation (preferably 1 to 3 or 6 to 12, more preferably 8 to 12), it is possible to perform surface coating on the surface of the toner mother particles while condensing the organosilicon compound. The condensation and surface coating are preferably carried out at 35°C or higher for 60 minutes or longer.

[0120] Also, a holding time at 35°C or higher may be provided before adjusting to the pH suitable for condensation. From the viewpoint of adjusting the macrostructure of the toner particle surface layer, the time is preferably 3 to 120 minutes.

[0121] Examples of the aqueous medium used in the suspension polymerization method include the following.

[0122] Water, alcohols such as methanol, ethanol, and propanol, and mixed solvents thereof.

[0123] As the dispersion stabilizer used when preparing the aqueous medium, a known inorganic compound dispersion stabilizer and an organic compound dispersion stabilizer can be used.

[0124] Examples of the dispersion stabilizer for inorganic compounds include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina.

[0125] On the other hand, examples of the dispersion stabilizer for organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, and starch. The amount of these dispersion stabilizers used is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

[0126] Among these dispersion stabilizers, when using a dispersion stabilizer for inorganic compounds, commercially available ones may be used as they are, but in order to obtain a dispersion stabilizer with a finer particle size, the inorganic compound may be generated in an aqueous medium. For example, in the case of tricalcium phosphate, it can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high stirring.

[0127] External additives may be externally added to the obtained toner particles to impart various properties to the toner. Examples of the external additives for improving the fluidity of the toner include inorganic fine particles such as silica fine particles, titanium oxide fine particles, and their complex oxide fine particles. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred.

[0128] Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halides, and wet silica produced from water glass.

[0129] Examples of the inorganic fine particles have few silanol groups on the surface and inside the silica fine particles, and Na2O, SO3 2-Less dry silica is preferred. Further, in the manufacturing process, the dry silica may be composite fine particles of silica and other metal oxides by using a metal halogen compound such as aluminum chloride and titanium chloride together with a silicon halogen compound.

[0130] By hydrophobically treating the surface of the inorganic fine particles with a treating agent, it is possible to achieve adjustment of the triboelectrification amount of the toner, improvement of environmental stability, and improvement of fluidity under high temperature and high humidity. Therefore, it is preferable to use hydrophobically treated inorganic fine particles.

[0131] Examples of the treating agent for hydrophobically treating the inorganic fine particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silicon compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. Among them, silicone oil is preferable. These treating agents may be used alone or in combination.

[0132] The total addition amount of the inorganic fine particles is preferably 1.00 part by mass or more and 5.00 parts by mass or less, more preferably 1.00 part by mass or more and 2.50 parts by mass or less, based on 100 parts by mass of the toner particles. From the viewpoint of the durability of the toner, the external additive preferably has a particle size of 1 / 10 or less of the average particle size of the toner particles.

[0133] Among the above-described toner manufacturing methods, (i) A step of preparing an aqueous medium in which particles containing a binder resin, a hydrocarbon wax, and a specific ester compound are dispersed, (ii) A step of mixing at least one monomer represented by the formula (A) and at least one monomer represented by the formula (B), and at least one monomer represented by the formula (C) and at least one monomer represented by the formula (D) to prepare a composition containing an organosilicon monomer, (iii) A step of mixing the composition containing the organosilicon monomer and the aqueous medium, and (iv) A step of polymerizing the composition containing the organosilicon monomer It is preferable that it is a method for producing a toner, which has the following in this order.

[0134] By using the above production method, a uniform organosilicon polymer can be uniformly formed on the surface of the toner particle matrix, and the effect of suppressing color unevenness is more remarkably exhibited.

[0135] Further, when producing a toner by the suspension polymerization method, for the purpose of distilling off the polymerizable monomer and solvent remaining after the polymerization reaction, it is preferable to raise the temperature of the aqueous medium and perform a distillation operation. Further, in the cooling step after the distillation, it is preferable to cool in a temperature range from a temperature equal to or higher than the melting point of the crystalline material to a temperature equal to or lower than the glass transition temperature of the binder resin at a rate of 20°C / min or more. By having a cooling rate of 20°C / min or more, the dispersibility of the crystalline material in the obtained toner particles is improved, and the low-temperature fixability is improved.

[0136] Hereinafter, the measurement methods for various physical properties in the present invention will be described.

[0137] <Measurement of the weight average particle diameter (D4) of toner or toner particles> The weight average particle diameter (D4) of the toner or toner particles is measured with a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube, and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data, and measured with an effective measurement channel number of 25,000 channels, and the measurement data is analyzed and calculated.

[0138] The electrolytic aqueous solution used for the measurement is a solution obtained by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0139] Note that before performing the measurement and analysis, the settings of the dedicated software are performed as follows.

[0140] In the "Standard Measurement Method (SOM) Change Screen" of the dedicated software, set the total count of the control mode to 50,000 particles, the number of measurements to 1 time, and set the Kd value to the value obtained using "Standard Particle 10.0μm" (manufactured by Beckman Coulter). By pressing the measurement button for the threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.

[0141] In the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0142] The specific measurement method is as follows. (1) Pour about 200 ml of the electrolytic aqueous solution into a 250 ml round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 rotations per second. Then, use the "Flash of Aperture Tube" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Pour about 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottom glass beaker, and add about 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant 3 times by mass with ion-exchanged water. (3) Place a predetermined amount of ion-exchanged water in the water tank of an ultrasonic disperser "UltrAsoniC Dispersion System TetorA150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and add about 2 ml of the Contaminon N to this water tank. (4) Set the beaker of (2) in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker of (4) with ultrasonic waves, add about 10 mg of toner or toner particles little by little to the electrolytic aqueous solution and disperse them. Then, continue the ultrasonic dispersion treatment for another 60 seconds. In ultrasonic dispersion, appropriately adjust so that the water temperature in the water tank is 10°C or higher and 40°C or lower. (6) Using a pipette, drop the electrolytic aqueous solution of (5) in which toner or toner particles are dispersed into the round-bottom beaker of (1) installed in the sample stand, and adjust so that the measurement concentration becomes about 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle diameter (D4). Note that when set to graph / volume% in the dedicated software, the "average diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle diameter (D4).

[0143] <Measurement of [SX2] and [SX1] of organosilicon polymer> The [SX2] and [SX1] of the organosilicon polymer are the 29 confirmed by Si-NMR (solid) measurement. The measurement conditions are shown below.

[0144] 「 29 Measurement conditions of Si-NMR (solid)」 Apparatus: JNM-ECX500II manufactured by JEOL RESONANCE Sample tube: 3.2 mm φ Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 97.38 MHz ( 29 Si) Reference substance: DSS (external standard: 1.534 ppm) Sample rotation speed: 10 kHz Contact time: 10 ms Delay time: 2 s Number of integrations: 2000 - 8000 times

[0145] After the above measurement, the tetrahydrofuran-insoluble content of toner particles is subjected to peak separation into the following X1 structure, X2 structure, X3 structure, and X4 structure with different substituents and bonding groups by curve fitting, and the peak area is calculated for each. X1 structure represented by formula (X1): (R 9 )(R 10 )(R 11 )SiO 1 / 2 X2 structure represented by formula (X2): (R 7 )(R 8 )Si(O 1 / 2 )2 X3 structure represented by formula (X3): R 17 Si(O 1 / 2 )3 X4 structure represented by formula (X4): Si(O 1 / 2 )4

[0146] The ratio of the peak area of the X2 structure to the total peak area of the organosilicon polymer was calculated as [SX2], and the ratio of the peak area of the X2 structure to the total peak area of the organosilicon polymer was calculated as [SX1].

[0147] <Measurement of the ratios of the (X2 - A) structure and the (X1 - A) structure in the (X2) structure and the (X1) structure of the organosilicon polymer> The ratios of the (X2 - A) structure and the (X1 - A) structure in the (X2) structure and the (X1) structure of the organosilicon polymer were determined by combining 29 the results of Si-NMR (solid) measurement of the tetrahydrofuran-insoluble content of the toner particles mentioned above, 13 C-NMR (solid) measurement, 1 H-NMR measurement to assign the functional groups bonded to Si and calculate the ratios.

[0148] Below 13 the measurement conditions of C-NMR (solid) are shown. Device: JNM-ECX500II manufactured by JEOL RESONANCE Sample tube: 3.2 mm φ Sample: 150 mg of the tetrahydrofuran-insoluble content of toner particles for NMR measurement Measurement temperature: Room temperature Pulse mode: CP / MAS Measured nuclear frequency: 123.25 MHz( 13 C) Reference substance: Adamantane (external standard: 29.5 ppm) Sample rotation speed: 20 kHz Contact time: 2 ms Delay time: 2 s Number of integrations: 1024 times

[0149] The signals due to methyl groups (Si-CH3), ethyl groups (Si-C2H5), propyl groups (Si-C3H7), butyl groups (Si-C4H9), pentyl groups (Si-C5H 11 ), hexyl groups (Si-C6H 13 ) bonded to silicon atoms, etc. are used to assign the functional groups, and the ratios of the (X2-A) structure and the (X1-A) structure in the (X2) structure and the (X1) structure of the organosilicon polymer are calculated.

[0150] <Measurement of the content Ces of the ester compound represented by formula (1) or (2) in the toner> The content Ces of the ester compound represented by formula (1) or (2) in the toner is measured by nuclear magnetic resonance spectroscopy( 1 H-NMR) [400 MHz, CDCl3, room temperature (25 °C)]. Measurement device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times

[0151] The content Chc of the ester compound in the toner is quantified from the integrated value of the spectrum of the plasticizer alone and the integrated value of the spectrum of the plasticizer in the spectrum of the toner.

[0152] <Measurement of the content Chc of the mold release agent (hydrocarbon wax) in the toner> The content Chc of the mold release agent (hydrocarbon wax) in the toner is measured by nuclear magnetic resonance spectroscopy ( 1 H-NMR) [400 MHz, CDCl3, room temperature (25 °C)]. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times

[0153] The content Chc of the mold release agent (hydrocarbon wax) in the toner is quantified from the integrated value of the spectrum of the plasticizer alone and the integrated value of the spectrum of the mold release agent in the spectrum of the toner.

Examples

[0154] Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited by the following examples. Example 36 is a reference example. In addition, "parts" in the text are based on mass unless otherwise specified.

[0155] <Preparation of polyester resin 1> Into an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, · 21.0 parts of terephthalic acid · 21.0 parts of isophthalic acid · 89.5 parts of bisphenol A-propylene oxide 2 mol adduct · 23.0 parts of bisphenol A-propylene oxide 3 mol adduct · 0.030 part of potassium titanyl oxalate The polyester monomer was charged, and the reaction was carried out at 220 °C for 15 hours under a nitrogen atmosphere and normal pressure, and then the reaction was carried out for 1 hour under a reduced pressure of 10 to 20 mmHg to obtain Polyester Resin 1. The glass transition temperature (Tg) of Polyester Resin 1 was 74.8 °C, and the acid value was 8.2 mgKOH / g.

[0156] <Ester Compound> The ester compounds used in the examples and comparative examples are shown in Table 1.

[0157]

Table 1

[0158] <Preparation of Hydrolysis Solution 1 of Organosilicon Monomer> 60.0 parts of ion-exchanged water was weighed into a reaction vessel equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass hydrochloric acid. This was heated while stirring to a temperature of 70 °C. Then, 40.0 parts of methyltriethoxysilane was added and stirred for 2 hours or more for hydrolysis. The end point of hydrolysis was confirmed visually by the fact that the oil and water did not separate and became a single layer, and it was cooled to obtain Hydrolysis Solution 1 of Organosilicon Monomer.

[0159] <Preparation of Hydrolysis Solutions 2 to 9 of Organosilicon Monomer> Hydrolysis Solutions 2 to 9 of Organosilicon Monomer were obtained in the same manner as the preparation method of Hydrolysis Solution 1 of Organosilicon Monomer, except that the formulation shown in Table 2 was changed for the purpose of making the molar concentration of the obtained hydrolysis solution constant.

[0160]

Table 2

[0161] <Preparation of Toner 1> (Preparation of Toner Base 1) Into a four-necked flask equipped with a reflux pipe, a stirrer, a thermometer, and a nitrogen inlet pipe, 700 parts of ion-exchanged water, 1000 parts of a 0.1 mol / L aqueous Na3PO4 solution, and 24.0 parts of a 1.0 mol / L aqueous HCl solution were added. While stirring at 12,000 rpm using a high-speed stirrer, a T.K. homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was maintained at 60°C. 85 parts of a 1.0 mol / L aqueous CaCl2 solution were gradually added thereto to prepare an aqueous dispersion containing fine water-insoluble dispersion stabilizer Ca3(PO4)2.

[0162] · 75.0 parts of styrene monomer · 25.0 parts of n-butyl acrylate · 0.5 part of hexanediol diacrylate · 6.5 parts of carbon black · 5.0 parts of polyester resin 1 · 0.7 part of charge control agent, Bontron E-88 (manufactured by Orient Chemical Industries Co., Ltd.) · 7.0 parts of mold release agent (Fisher-Tropsch wax, melting point: 79°C) · 21.0 parts of plasticizer (ester compound 1) The polymerizable monomer composition obtained by dispersing the above materials in an attritor (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) for 3 hours was maintained at 60°C for 20 minutes. Thereafter, 12.0 parts (40% toluene solution) of t-butyl peroxy pivalate, a polymerization initiator, was added to the polymerizable monomer composition, and the resulting polymerizable monomer composition was introduced into the above aqueous medium. Granulation was carried out for 10 minutes while maintaining the rotational speed of the high-speed stirrer at 12,000 rpm.

[0163] Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70°C, and the mixture was reacted for 5 hours while stirring slowly to obtain an aqueous medium in which toner mother body 1 was dispersed. The pH of this aqueous medium was 5.1.

[0164] (Preparation of Composition 1 Containing Organosilicon Monomer) Into a container such as a glass beaker, the hydrolysis solution of the following organosilicon monomer was introduced and stirred and mixed at room temperature to prepare Composition 1 containing an organosilicon monomer. · 18.0 parts of the hydrolysis solution of the organosilicon monomer · 12.0 parts of the hydrolysis solution of the organosilicon monomer

[0165] (Preparation of Toner 1) A container containing the aqueous medium in which the aforementioned toner mother body 1 was dispersed was heated to an internal temperature of 55°C, and the entire amount of Composition 1 containing the organosilicon monomer was added to start the formation of the toner surface layer. After holding for 30 minutes as it was, the slurry was adjusted to pH = 9.0 for condensation completion using an aqueous sodium hydroxide solution and held for another 5 hours to form the surface layer. Then, the reflux pipe was removed, a device for recovering the distillate was attached, and the temperature was raised until the internal temperature reached 100°C. A distillation operation was performed while maintaining the internal temperature at 100°C for 5 hours to distill off the residual monomers and other solvents. After the distillation was completed, it was cooled to 30°C at a rate of 0.5°C / min, and 10% hydrochloric acid was added to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain toner particles 1 with a weight average particle size of 6.1 μm. The obtained toner particles 1 were used as Toner 1.

[0166] The formulation and manufacturing conditions of Toner 1 were shown in Table 3, and the physical properties were shown in Table 4.

[0167] <Preparation of Toners 2 - 36, 39 - 44> Toners 2 - 36, 39 - 44 were obtained in the same manner as Toner 1 except that the formulation and conditions shown in Table 3 were changed. The formulation and manufacturing conditions of the obtained toners were shown in Table 3, and the physical properties were shown in Table 4.

[0168] <Preparation of Toner 37> (Preparation of Toner Mother Body 37) 700 parts of ion-exchanged water, 1000 parts of 0.1 mol / liter aqueous Na3PO4 solution, and 24.0 parts of 1.0 mol / liter aqueous HCl solution were added into a four-necked flask equipped with a reflux pipe, a stirrer, a thermometer, and a nitrogen inlet pipe, and while stirring at 12,000 rpm using a high-speed stirring device T.K. Homomixer (Special Machine Chemical Industry Co., Ltd.), it was maintained at 60°C. 85 parts of 1.0 mol / liter aqueous CaCl2 solution were gradually added here to prepare an aqueous dispersion containing fine water-insoluble dispersion stabilizer Ca3(PO4)2.

[0169] · Styrene monomer: 75.0 parts · n-Butyl acrylate: 25.0 parts · Hexanediol diacrylate: 0.5 part · Carbon black: 6.5 parts · Polyester resin 1: 5.0 parts · Charge control agent, Bontron E-88 (manufactured by Orient Chemical Industries Co., Ltd.): 0.7 part · Release agent (Fisher-Tropsch wax, melting point: 79°C): 7.0 parts · Plasticizer (ester compound 1): 21.0 parts · Dimethyldimethoxysilane: 3.7 parts The polymerizable monomer composition obtained by dispersing the above materials in an attritor (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) for 3 hours was held at 60°C for 20 minutes. Then, 12.0 parts (40% toluene solution) of t-butylperoxypivalate, which is a polymerization initiator, was added to the polymerizable monomer composition, and the resulting polymerizable monomer composition was introduced into the above aqueous medium, and granulation was carried out for 10 minutes while maintaining the rotational speed of the high-speed stirrer at 12,000 rpm.

[0170] Thereafter, the high-speed stirrer was changed to a propeller-type stirrer, the internal temperature was raised to 70°C, and the mixture was reacted for 5 hours with slow stirring to obtain an aqueous medium in which the toner mother body 37 was dispersed. The pH of this aqueous medium was 5.0.

[0171] (Preparation of toner 37) An aqueous sodium hydroxide solution was added to the aqueous medium in which the aforementioned toner mother body 37 was dispersed, adjusted to pH 9.0, and held at 70°C for 3 hours. Then, 8.0 parts of the hydrolysis solution 1 of the organosilicon monomer was added, and the mixture was further held for 5 hours to form a surface layer. Thereafter, the reflux pipe was removed, a device for recovering the distillate was attached, and the temperature was raised until the internal temperature reached 100°C. A distillation operation was performed while maintaining the internal temperature at 100°C for 5 hours to distill off the residual monomers and other solvents. After the distillation was completed, the mixture was cooled to 30°C at a rate of 0.5°C / min, and then 10% hydrochloric acid was added to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain toner particles 37 having a weight average particle diameter of 6.3 μm. The obtained toner particles 37 were designated as toner 37.

[0172] <Preparation of Toner 38> To 100 parts of the toner base, 1.80 parts of hydrophobic silica having a specific surface area of 90 m 2 / g by the BET method and having its surface hydrophobized with 3.0 mass% of hexamethyldisilazane and 3 mass% of 100 cP silicone oil were mixed in a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) to obtain Toner 38. The physical properties of Toner 38 are shown in Table 4.

[0173]

Table 3

[0174]

Table 4

[0175] <Toner Evaluation> A Canon laser beam printer LBP9600C was modified so that the fixing temperature and the process speed could be adjusted, and the following evaluations were carried out.

[0176] 〔Low-temperature Fixing Property〕 In an environment of normal temperature and normal humidity (25°C / 50%RH), at a process speed of 320 mm / sec, the fixing temperature was changed in increments of 3°C, and a solid image (toner loading: 0.40 mg / cm 2 ) was formed. As the transfer material, ordinary paper (XEROX 4200 paper of LETTER size, manufactured by XEROX, 75 g / m 2 ) was used.

[0177] Using Kimwipe [S-200 (manufactured by Kurecia Co., Ltd.)], a load of 75 g / Cm 2 was applied to rub the fixed image 10 times, and the evaluation of the low-temperature fixing property was carried out at a temperature at which the density reduction rate before and after rubbing was less than 5%. The image density was measured with a reflection densitometer (product name: RD918, manufactured by Macbeth).

[0178] In the present invention, C or higher was judged to have good low-temperature fixing property.

[0179] (Evaluation Criteria) A: Below 130°C B: 133°C or higher and 139°C or lower C: 142°C or higher and 148°C or lower D: 151°C or higher and 160°C or lower E: 163°C or higher

[0180] 〔Durability〕 Durability was determined by measuring fogging through the following procedure.

[0181] In a high-temperature and high-humidity environment (temperature 33°C / humidity 85%RH), after printing out 15,000 images with a 1% printing rate marked by a horizontal line and leaving them for 24 hours, the reflectance (%) of the non-image part of the printed-out images was measured using "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.).

[0182] The obtained reflectance was evaluated using the value (%) obtained by subtracting the reflectance (%) of unused printout paper (standard paper) measured in the same manner from it. The smaller the value, the more the image fogging is suppressed. The evaluation was carried out in the gloss paper mode using plain paper (HP Brochure Paper 200g, Glossy, manufactured by HP, 200 g / m 2 ). In the present invention, C or higher was judged to have good durability.

[0183] (Evaluation Criteria) A: Less than 0.5% B: 0.5% or higher and less than 1.5% C: 1.5% or higher and less than 3.0% D: 3.0% or higher

[0184] 〔Color unevenness〕 At room temperature and normal humidity (25°C / 50%RH), at a process speed of 160 mm / sec, at a temperature at which the density reduction rate before and after rubbing measured in the above evaluation of low-temperature fixing property is less than 5%, for a solid image (toner loading amount: 0.40 mg / cm 2) was formed. The evaluation paper was HP Brochure Paper 200g, Glossy, (manufactured by HP, 200g / m 2 ) was used.

[0185] The L values at a total of 9 points at the upper end, the center, and the lower end of the obtained solid image paper were * a * b * coordinates in the space (CIE1976) (a * , b * ) were measured using a colorimeter (for example, Spectro Lino, manufactured by Sakata Inx Engineering Co., Ltd.).

[0186] The color differences ΔE on the a * , b * plane between each point were calculated, and the maximum color difference among them was taken as ΔE*max and used as an index of color unevenness in the present invention. In the present invention, C or more was judged as good color unevenness.

[0187] (Evaluation criteria) A: ΔE*max is less than 1.0 B: ΔE*max is 1.0 or more and less than 2.0 C: ΔE*max is 2.0 or more and less than 3.0 D: ΔE*max is 3.0 or more and less than 4.0 E: ΔE*max is 4.0 or more

[0188] 〔Environmental stability〕 The environmental stability was judged by measuring fogging according to the following procedure.

[0189] In a high-temperature and high-humidity environment (temperature 33°C / humidity 85%RH), after printing out 1000 images with a printing rate of 1% with a horizontal line and leaving them for one week, the reflectance (%) of the non-image part of the printed-out image was measured with a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.).

[0190] The obtained reflectance was evaluated using the value (%) obtained by subtracting the reflectance (%) of unused printed paper (standard paper) measured in the same manner. The smaller the value, the more the image fogging is suppressed. The evaluation was performed in the gloss paper mode using plain paper (HP Brochure Paper 200g, Glossy, manufactured by HP, 200g / m 2 ).

[0191] Toner with poor environmental stability is likely to adsorb moisture on the surface when left in a high-temperature and high-humidity environment for a long time, resulting in a decrease in chargeability and an increased tendency to cause fogging. In the present invention, C or more was judged to have good environmental stability.

[0192] (Evaluation Criteria) A: Less than 0.5% B: 0.5% or more and less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more

[0193] [Examples 1 to 37] In Examples 1 to 37, the above-described evaluation was performed using Toners 1 to 37, respectively. The evaluation results are shown in Table 5.

[0194] [Comparative Examples 1 to 7] In Comparative Examples 1 to 7, the above-described evaluation was performed using Toners 38 to 44, respectively. The evaluation results are shown in Table 5.

[0195] [Table 5]

Claims

1. A toner having toner particles with a surface layer containing an organosilicon polymer, wherein the toner particles contain a binder resin, a hydrocarbon wax, and an ester compound represented by the following formula (1) or (2), 【Chemical 1】 (In the above formula (1) and the above formula (2), R 1 and R 4 represent an alkylene group having 1 to 6 carbon atoms, and R 2 , R 3 , R 5 and R 6 each independently represent a linear alkyl group having 11 to 25 carbon atoms.) the organosilicon polymer has at least one partial structure represented by the following formula (X2) and at least one partial structure represented by the following formula (X1), 【Chemical Formula 2】 (In the above formula (X2) and the above formula (X1), R 7 to R 11 each independently represents an organic group bonded to a silicon atom, a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group.) a partial structure of the organosilicon polymer other than the partial structure represented by the formula (X2) and the partial structure represented by the formula (X1) is at least one partial structure represented by the following formula (X3-A) and at least one partial structure represented by the following formula (X4-A), 【Chem.】 (In the formula (X3-A), R17 represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom.) The tetrahydrofuran-insoluble content of the toner particles 29 In the measurement of Si-NMR, when the ratio of the peak area of the partial structure represented by the formula (X2) to the total peak area of the organosilicon polymer is [SX2], and the ratio of the peak area of the partial structure represented by the formula (X1) is [SX1], the [SX2] and the [SX1] are 30% ≤ [SX2] + [SX1] ≤ 90% satisfying, a toner characterized by this.

2. Among the partial structure represented by the formula (X2) and the partial structure represented by the formula (X1), the total proportion of the partial structure represented by the following formula (X2-A) and the partial structure represented by the following formula (X1-A) is 80% or more, the toner according to claim 1. [Chemical Formula 3] (In the formula (X2-A) and the formula (X1-A), R 12 to R 16 each independently represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom.)

3. The [SX2] and the [SX1] are, 60% ≤ [SX2] + [SX1] ≤ 90% satisfying, the toner according to claim 1 or 2.

4. The toner particles have a mother particle and the surface layer on the surface of the mother particle, the mother particle contains the binder resin, the hydrocarbon wax, and the ester compound represented by the formula (1) or (2), the toner according to any one of claims 1 to 3.

5. The organosilicon polymer is a polymer of a composition containing at least one monomer represented by the following formula (A) and at least one monomer represented by the following formula (B), the toner according to any one of claims 1 to 4. 【Chemical Formula 5】 (In the above formula (A) and the above formula (B), R 18 , R 19 , R 20 , R 22 , R 23 each independently represents a saturated aliphatic hydrocarbon group or aryl group having 1 to 6 carbon atoms bonded to a silicon atom. R 21 , R 24 , R 25 each independently represents a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group.)

6. The organosilicon polymer is a polymer of a composition containing at least one monomer represented by the formula (A) and at least one monomer represented by the formula (B), and at least one monomer represented by the following formula (C) and at least one monomer represented by the following formula (D), the toner according to claim 5. 【Chemical Formula 6】 (In the formula (C) and the formula (D), R 26 represents a saturated aliphatic hydrocarbon group or an aryl group having 1 to 6 carbon atoms bonded to a silicon atom. R 27 to R 33 each independently represents a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group.)

7. A method for manufacturing the toner according to claim 6, the manufacturing method is, (i) A step of preparing an aqueous medium in which particles containing a binder resin, a hydrocarbon wax, and the ester compound are dispersed. Step (ii) of mixing at least one monomer represented by the formula (A) and at least one monomer represented by the formula (B), and at least one monomer represented by the formula (C) and at least one monomer represented by the formula (D) to prepare a composition containing an organosilicon monomer; Step (iii) of mixing the composition containing the organosilicon monomer with the aqueous medium; and Step (iv) of polymerizing the composition containing the organosilicon monomer; A method for producing a toner, which comprises these steps in this order.

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