toner

Abstract

To provide a toner that can prevent embedding of an external additive, and can achieve both low temperature fixability and transfer properties.SOLUTION: A toner has a toner particle that contains a binder resin and organic silicon polymer particles on a surface of the toner particle. The binder resin contains a crystalline resin. When TE (MPa) is the Young's modulus measured by a micro compression tester at 25°C by using a test piece obtained by pelletizing the toner, and SiE (MPa) is the Young's modulus measured by the micro compression tester at 25°C by using one particle of the organic silicon polymer particles separated from the toner, The TE and the SiE satisfy 800≤TE≤2500 and 1.5≤SiE / TE≤10.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to toner used in electrophotographic, electrostatic recording, electrostatic printing, and toner jet systems. [Background technology]

[0002] In recent years, electrophotographic devices such as full-color printers and full-color copiers have been increasingly required to offer added value such as high productivity, high image quality, and high stability. To meet these demands and obtain full-color images at higher speeds, the so-called tandem method is widely adopted, in which multiple electrophotographic photoreceptors are arranged in series, and the images of each component are superimposed on an intermediate transfer medium for simultaneous transfer. In the tandem method, the transfer performance is even more important because it involves two transfer processes: primary transfer from the photoreceptor to the intermediate transfer medium and secondary transfer from the intermediate transfer medium to the recording material. On the other hand, in order to achieve high productivity, it is important to melt the toner more quickly in the fixing process. A known technology involves using a crystalline resin with excellent sharp-melt properties as the main component of the toner binder resin. For example, Patent Document 1 proposes a toner that improves low-temperature fixability and offset resistance by using a crystalline polyester containing a divalent or higher carboxylic acid having a sulfonic acid group as a copolymer component. Furthermore, Patent Document 2 proposes a toner that achieves both low-temperature fixability and heat-resistant storage by using an acrylate-based resin with crystalline side chains. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2001-305796 [Patent Document 2] Japanese Patent Publication No. 2014-130243 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, in any of the above methods, the crystalline resin, which is the main component of the toner, has a lower Young's modulus compared to the amorphous resin. Therefore, when image output is performed over a long period of time, external additives are likely to be embedded in the toner particles. When the external additives are embedded in the toner particles, a matrix with high adhesion is exposed, so the transferability of the toner particles to the intermediate transfer body tends to decrease. Therefore, it is necessary to develop a toner that can achieve both low-temperature fixing properties and transferability even when using a crystalline resin as the main component and performing image output over a long period of time. An object of the present invention is to provide a toner that solves the above problems. Specifically, by using an external additive having an appropriate range of Young's modulus with respect to the Young's modulus of the toner, it is possible to suppress the embedding of the external additive and provide a toner that can achieve both low-temperature fixing properties and transferability.

Means for Solving the Problems

[0005] The present invention is a toner containing toner particles containing a binder resin and having organosilicon polymer particles on the surface of the toner particles, where the binder resin contains a crystalline resin, When using a test piece obtained by pelletizing the toner, at 25°C, the Young's modulus measured by a micro-compression tester is defined as TE (MPa), and when using one particle of the organosilicon polymer particles separated from the toner, at 25°C, the Young's modulus measured by a micro-compression tester is defined as SiE (MPa), the TE and the SiE satisfy 800≦TE≦2500 1.5≦SiE / TE≦10.0 and relates to a toner characterized by satisfying the above conditions.

Effects of the Invention

[0006] According to the present invention, since the ratio of the Young's modulus of the toner to the Young's modulus of the organosilicon polymer particles is within a specified range, even when image output is performed over a long period of time, the embedding of the external additive is suppressed. As a result, it is possible to provide a toner that can achieve both low-temperature fixing properties and transferability.

Mode for Carrying Out the Invention

[0007] In the present invention, the description of "XX or more and XX or less" or "XX to XX" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified.

[0008] In the present invention, (meth)acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.

[0009] In the present invention, "monomer unit" means one section of a carbon-carbon bond in the main chain where vinyl monomers in a polymer are polymerized, and is taken as one unit. The vinyl monomer can be represented by the following formula (Z).

[0010] [Chemical formula] [In formula (Z), R Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R Z2 represents an arbitrary substituent.]

[0011] In the present invention, the crystalline resin refers to a resin that shows a distinct endothermic peak in differential scanning calorimetry (DSC) measurement.

[0012] Hereinafter, the mode for carrying out the present invention will be described in detail.

[0013] The present invention relates to toner particles containing a binder resin and a toner having organosilicon polymer particles on the surface of the toner particles, where the binder resin contains a crystalline resin, using a test piece obtained by pelletizing the toner, at 25°C, when the Young's modulus measured by a micro-compression tester is defined as TE (MPa), and using one particle of the organosilicon polymer particles separated from the toner, at 25°C, when the Young's modulus measured by a micro-compression tester is defined as SiE (MPa), the TE and the SiE are 800 ≤ TE ≤ 2500 1.5 ≤ SiE / TE ≤ 10.0 It is characterized by satisfying the following conditions.

[0014] As a result of diligent research by the present inventors, we have found that the above problem can be solved by controlling the ratio of the Young's modulus of a toner containing crystalline resin to the Young's modulus of organosilicon polymer particles present on the surface of the toner particles, and thus arrived at the present invention.

[0015] The inventors speculate that the reason they were able to solve the above problem is as follows:

[0016] When the main component of toner is a crystalline resin, the toner tends to have a low Young's modulus. Furthermore, large-particle silica particles, conventionally used to improve transferability through the spacer effect, are composed solely of siloxane bonds (Si-O-Si), resulting in a very high crosslink density and a hard texture. Therefore, when using toners that combine these elements to print low-density images over long periods, the silica particles tend to become embedded in the toner particle surface. In particular, in two-component developers where toner and carrier are mixed, the carrier and silica particles on the toner surface rub against each other, causing mechanical stress that can easily lead to the silica particles becoming embedded in the toner particle surface.

[0017] On the other hand, organosilicon polymer particles have Si-OC bonds in addition to siloxane bonds (Si-O-Si), and the Young's modulus can be adjusted by controlling the content ratio of these bonds. Therefore, the Young's modulus of the organosilicon polymer particles can be controlled relative to the Young's modulus of the toner, whose main component is crystalline resin, and by keeping the ratio of the two within a predetermined range, it is possible to suppress the crushing and embedding of the organosilicon polymer particles.

[0018] When measuring the Young's modulus (TE) at 25°C using a test piece obtained by pelletizing toner, the TE must be between 800 MPa and 2500 MPa. If the TE is less than 800 MPa, the Young's modulus of the toner is too low, causing the toner to deform and coalesce due to stress with components such as carriers, resulting in toner agglomeration and image defects. On the other hand, if the TE exceeds 2500 MPa, deformation is less likely to occur during the fixing process, and sufficient low-temperature fixing performance cannot be achieved.

[0019] Furthermore, in this invention, when the Young's modulus measured using one organosilicon polymer particle separated from the toner at 25°C with a microcompression tester is defined as SiE (MPa), it is necessary that TE and SiE satisfy the condition 1.5 ≤ SiE / TE ≤ 10.0. If SiE / TE is less than 1.5, the organosilicon polymer particle is too soft relative to the toner, and the organosilicon polymer particle will collapse due to stress with components such as carriers.

[0020] On the other hand, if the SiE / TE ratio exceeds 10.0, the organosilicon polymer particles are too hard relative to the toner, and stress from the carrier and other components causes the organosilicon polymer particles to become embedded in the toner particles. Details on how to measure TE and SiE will be described later.

[0021] The crystalline resin content is preferably 50% by mass or more, based on the binder resin. When the crystalline resin content is 50% by mass or more, the proportion of crystalline resin is sufficiently high, making it easier to obtain good low-temperature fixation properties.

[0022] Furthermore, in the present invention, it is preferable that the crystalline resin has diffraction peaks in the X-ray diffraction spectrum using CuKα rays, where the diffraction angle 2θ is in the range of 20.0° to 22.0°. When a crystalline resin having diffraction peaks in this range is used, the hardness of the toner is improved, the embedding of external additives is suppressed, and the transferability is improved. The method for measuring X-ray diffraction will be described later.

[0023] In the present invention, it is preferable that the toner has a matrix-domain structure in which amorphous resin domains are dispersed in a crystalline resin matrix. Having such a structure allows for a favorable balance between improved low-temperature fixation and suppression of embedding of external additives.

[0024] In the toner of the present invention, domains containing amorphous resin are preferably located on the surface of the toner particles, which is effective in suppressing the embedding of external additives. Specifically, they are preferably located within 800 nm from the surface of the toner particles. In this case, it is more preferable that the number-average particle size of the domains is 20 nm or more and 500 nm or less.

[0025] If the average particle size of the domains is within the above range, it is possible to achieve both improved adhesion and suppression of embedding of external additives. Observation of the toner particle cross-section and measurement of the matrix domain structure will be described later.

[0026] The average circularity of the toner is preferably between 0.930 and 0.980. If the average circularity of the toner is within this range, the mechanical stress from components such as the carrier will be distributed evenly, suppressing a decrease in transferability even after durability has been maintained. The method for measuring the average circularity of the toner will be described later.

[0027] <Description of materials> The following describes in detail the materials that can be used to carry out the present invention.

[0028] <Binding resin> The binder resin of the present invention must have a crystalline resin.

[0029] As the crystalline resin, known crystalline resins can be used. Examples include crystalline vinyl resin, crystalline polyester, crystalline polyurethane, and crystalline polyurea. Also, ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, and ethylene-acrylic acid copolymer can be used.

[0030] From the viewpoint of low-temperature fixation properties, crystalline vinyl resin and crystalline polyester are preferred, and crystalline vinyl resin is particularly preferred.

[0031] The crystalline vinyl resin preferably has a first monomer unit represented by the following formula (1). Having a monomer unit represented by the following formula (1) in the crystalline resin increases the crystallinity of the crystalline material, improves the hardness of the toner against external forces, suppresses the embedding of external additives, and improves transferability.

[0032] [ka] [In formula (1), R Z1 R represents a hydrogen atom or a methyl group. 1 This represents an alkyl group with 18 to 36 carbon atoms.

[0033] The first monomer unit represented by formula (1) above is derived from a first polymerizable monomer selected from the group consisting of (meth)acrylic acid esters having an alkyl group with 18 to 36 carbon atoms. The crystalline resin having the first monomer unit represented by formula (1) above has a comb-shaped crystalline structure, which strengthens the crystalline structure, makes it easier to suppress the embedding of external additives, and improves transferability.

[0034] Examples of (meth)acrylic acid esters having an alkyl group with 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, myricyl (meth)acrylate, dotriacontane (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group with 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].

[0035] Of these, from the viewpoint of low-temperature fixability, (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms are preferred. More preferably, (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms are preferred. Even more preferably, at least one selected from the group consisting of linear (meth)acrylic acid stearyl and (meth)acrylic acid behenyl. The polymerizable monomer that produces the first monomer unit represented by formula (1) above may be used alone or in combination of two or more types.

[0036] The proportion of the first monomer unit is preferably 30.0% by mass or more, and more preferably 50.0% by mass or more, relative to the total mass of all monomer units in the crystalline resin. It is also preferably 95% by mass or less, and more preferably 90% by mass or less.

[0037] The crystalline vinyl resin preferably has a second monomer unit represented by the following formula (2) or formula (3), which is different from the first monomer unit.

[0038] [ka] (In the formula, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.) R 3 teeth, Nitrile group, -C(=O)NHR 10 (R 10 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.). hydroxy group, -COOR 31 (R 31 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.). -NH-C(=O)-N(R 33 )2(R 33 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.). -COO(CH2)2NHCOOR 34 (R 34 represents an alkyl group having 1 to 4 carbon atoms.), or -COO(CH2)2-NH-C(=O)-N(R 35 )^{2}(R 35 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.). represents, R 4 represents a hydrogen atom or a methyl group.).

[0039] [Chemical formula] (In the formula, R 5 represents an alkyl group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom or a methyl group.).

[0040] By having the second monomer unit, a polarity difference occurs with the first monomer unit.

[0041] This difference in polarity promotes the crystallization of the first monomer unit. As a result, the hardness of the toner against external forces is improved, the embedding of external additives is suppressed, and the transferability is improved. Specifically, the first monomer unit is incorporated into the crystalline resin, and crystallinity is exhibited by the aggregation of the first monomer units. Normally, the crystallization of the first monomer unit is inhibited if other monomer units are incorporated, making it difficult for the crystalline resin to exhibit crystallinity. This tendency is particularly pronounced when multiple types of monomer units are randomly bonded within a single molecule of the crystalline resin. However, by having a first monomer unit and a second monomer unit with a difference in polarity, it is thought that the first monomer unit and the second monomer unit can form a clear phase separation state without being incompatible in the crystalline resin. As a result, it becomes possible to enhance crystallinity even when other monomer units are incorporated, improving the hardness of the toner against external forces, suppressing the embedding of external additives, and improving the transferability.

[0042] Specifically, as the polymerizable monomer that produces the second monomer unit, for example, a polymerizable monomer that satisfies formula (2) above can be used from among the polymerizable monomers listed below.

[0043] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.

[0044] Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0045] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

[0046] Monomers having a urea group: For example, monomers obtained by reacting a carbon 3-22 amine [primary amines (n-butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.)] with a carbon 2-30 isocyanate having an ethylenically unsaturated bond by known methods.

[0047] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0048] In particular, monomers having a nitrile group, an amide group, a hydroxyl group, or a urea group are preferred. More preferably, monomers having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxyl group, and a urea group, and an ethylenically unsaturated bond. Acrylonitrile and methacrylonitrile are especially preferred.

[0049] Furthermore, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octoate are also preferably used as polymerizable monomers to produce a second monomer unit. Among these, vinyl esters are preferred from the viewpoint of low-temperature fixability because they are non-conjugated monomers, their reactivity with the first polymerizable monomer is easily maintained at an appropriate level, and the crystallinity of the polymer is easily improved.

[0050] The proportion of the second monomer unit is preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less, relative to the total mass of all monomer units of the crystalline resin.

[0051] The mixture may also contain a third monomer unit derived from a third polymerizable monomer, provided that the mass ratio of the first monomer unit and the second monomer unit described above is not impaired.

[0052] As a third polymerizable monomer, the following monomers can also be used, for example.

[0053] Styrene, o-methylstyrene and other styrenes and their derivatives, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among these, the third polymerizable monomer is preferably styrene from the viewpoint of low-temperature fixability.

[0054] The proportion of the third monomer unit is preferably 5.0% by mass or more and 50.0% by mass or less, and more preferably 10.0% by mass or more and 30.0% by mass or less, relative to the total mass of all monomer units of the crystalline resin.

[0055] <Amorphous resin> The binder resin may contain an amorphous resin. The inclusion of an amorphous resin allows for the formation of domains. The amorphous resin can be any known amorphous resin, and from the viewpoint of low-temperature fixation and fixation separation, it is preferably polyester, styrene-acrylic resin, or a hybrid resin thereof.

[0056] As the styrene-acrylic resin, a styrene-acrylic resin commonly used in toners can be suitably used.

[0057] Examples of styrene monomers 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, and p-phenylstyrene. These styrene monomers can be used individually or in combination.

[0058] Examples of (meth)acrylic monomers include 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, and maleic acid. These (meth)acrylic monomers can be used individually or in combination.

[0059] As the polyester, polyester commonly used in toners can be suitably used. Examples of monomers used in polyester include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters.

[0060] Examples of polyhydric alcohols include the following:

[0061] Examples of dihydric alcohols include the following bisphenol derivatives.

[0062] Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, etc.

[0063] Other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

[0064] These polyhydric alcohols can be used individually or in combination.

[0065] Examples of polycarboxylic acids include the following:

[0066] Examples of divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferably used.

[0067] Examples of trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include the following:

[0068] 1,2,4-Benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimeric acid, their acid anhydrides, or their lower alkyl esters. Of these, 1,2,4-Benzenetricarboxylic acid (trimellitic acid) or its acid anhydrides and other derivatives are preferred because they are inexpensive and easy to control the reaction.

[0069] These polycarboxylic acids can be used individually or in combination.

[0070] <Other resins> The binder resin may contain resins other than crystalline resins and amorphous resins to an extent that does not impair the effects of the present invention, for purposes such as improving pigment dispersibility.

[0071] Examples of such resins include the following:

[0072] Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, polyvinyl acetate, silicone resin, polyester, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin.

[0073] <Organosilicon polymer particles> The method for producing the organosilicon polymer particles used in the present invention is not particularly limited, but it is preferable to form the particles by hydrolysis and condensation polymerization of a silane monomer using the sol-gel method. Specifically, particles are formed by polymerizing a mixture of a bifunctional monomer (S2) having two siloxane bonds, a trifunctional monomer (S3) having three siloxane bonds, and a tetrafunctional monomer (S4) having four siloxane bonds through hydrolysis and condensation polymerization. The inventors have produced organosilicon polymer particles that exhibit the above effects by adjusting the mixing ratio of the above monomers, the solvent temperature during the hydrolysis and condensation reactions, the type of catalyst, the stirring time, and the pH of the solution in the production method.

[0074] The monomers used in this invention can be appropriately selected based on their compatibility with the solvent and catalyst, or their hydrolyzability, but tetraethoxysilane is preferred as the tetrafunctional monomer. Trimethoxymethylsilane is preferred as the trifunctional monomer. Dimethyldimethoxysilane is preferred as the difunctional monomer.

[0075] [ka]

[0076] [ka]

[0077] [ka] (Rd and Re represent alkyl groups with 1 to 6 carbon atoms, respectively.)

[0078] The number-average diameter of the primary particles of the organosilicon polymer is preferably between 20 nm and 300 nm. When the number-average diameter of the primary particles is within this range, the organosilicon polymer particles, which are an external additive, can uniformly coat the toner particles, and detachment can be effectively suppressed. Furthermore, stress on the toner can be suppressed, improving transferability after durability.

[0079] The number-average diameter of the primary particles of the organosilicon polymer particles is more preferably 50 nm to 250 nm, and even more preferably 80 nm to 180 nm from the above viewpoint.

[0080] The content of organosilicon polymer particles is preferably 0.5 parts by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of toner particles. If the content of organosilicon polymer particles is within the above range, the coating rate of organosilicon polymer particles is appropriate for a sufficient amount of toner, thus reducing stress during durability. Furthermore, it does not hinder heat conduction to the matrix.

[0081] The organosilicon polymer particles of the present invention are 29 In the chart obtained by Si-NMR measurement, the total peak area originating from organosilicon polymers is designated as SA, SiO 4 / 2 The peak area derived from the unit (derived from Q units) is S4, SiO 3 / 2 The peak area derived from the unit (derived from T units) is S3, SiO 2 / 2 When the peak area derived from a unit (derived from D units) is denoted as S2, 0.20 ≤ S4 / SA ≤ 0.60 0.00 ≤ S3 / SA ≤ 0.50 0.20 ≤ S² / SA ≤ 0.70 It is preferable that the above conditions are met. Within the above range, when the toner is subjected to stress from components such as the carrier, the embedding of external additive particles into the toner particle surface and the destruction of the external additive particles themselves can be suppressed. Furthermore, 0.30 ≤ S4 / SA ≤ 0.50 0.00 ≤ S3 / SA ≤ 0.10 0.50 ≤ S² / SA ≤ 0.70 This results in an optimal ratio of Si-OC bonds to siloxane bonds (Si-O-Si) within the external additive particles, which is more preferable from the viewpoint of toner durability and stability. 29 The method for measuring the abundance ratio of organosilicon polymer particles using Si-NMR will be described later.

[0082] It is preferable that the surface of the organosilicon polymer particles is treated with a hydrophobic agent. The hydrophobic agent is not particularly limited, but it is preferably an organosilicon compound. Examples include alkylsilazane compounds such as hexamethyldisilazane, alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, and octamethylcyclotetrasiloxane, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, or silicone oils and silicone varnishes. Hydrophobic treatment of the surface of the external additive particles suppresses aggregation of external additives, allows for uniform coating of toner particles, and further improves transferability after durability. Among these, it is preferable that the particles be treated with at least one compound selected from the group consisting of alkylsilazanes, alkylalkoxysilanes, chlorosilanes, and silicone oils. Furthermore, treatment with alkylsilazane is more preferable from the viewpoint of transferability after durability.

[0083] <Inorganic fine particles> The toner of the present invention may optionally contain inorganic fine particles.

[0084] Inorganic fine particles may be internally added to toner particles, or externally added to toner particles as an additive other than organosilicon polymer particles. Examples of inorganic fine particles include silica fine particles, titanium dioxide fine particles, alumina fine particles, or complex oxide fine particles thereof. Among inorganic fine particles, silica fine particles and titanium dioxide fine particles are preferred for improving fluidity and uniformizing charge.

[0085] Inorganic fine particles are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof.

[0086] From the perspective of improving fluidity, inorganic fine particles as an external additive have a specific surface area of ​​50 m². 2 / g or more 400m 2 It is preferable that the amount is less than or equal to / g. Furthermore, from the viewpoint of improving durability and stability, the inorganic fine particles used as an external additive should have a specific surface area of ​​10 m². 2 / g or more 50m 2 It is preferable that the amount is less than or equal to / g. In order to achieve both improved fluidity and durability stability, inorganic fine particles may be used in combination.

[0087] The content of external additives other than organosilicon polymer particles is preferably 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles. Mixing of toner particles and external additives can be done using a known mixer such as a Henschel mixer.

[0088] <Release agent> The toner particles may contain a release agent, and the release agent is selected to be optimal in combination with the crystalline resin. In the toner of the present invention, it is thought that the release agent migrates to the toner surface via the crystalline resin during fixing, so a release agent having a melting point greater than or equal to the melting point Tp of the crystalline resin is preferred. Examples of release agents include the following.

[0089] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and deoxidized fatty acid esters such as deoxidized carnauba wax, which have been partially or completely deoxidized.

[0090] Furthermore, the following can be listed: Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, hexamethylene Saturated fatty acid bisamides such as bis-stearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyl adipic acid amide, and N,N'dioleyl sebacinamide; aromatic bisamides such as m-xylenebis-stearamide and N,N'distearyl isophthalamide; aliphatic metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and fats.

[0091] The release agent content is preferably 2.0 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the binder resin.

[0092] <Coloring agent> Toner particles may contain colorants as needed. Examples of colorants include:

[0093] Examples of black colorants include carbon black and black colorants prepared by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, using dyes and pigments in combination is preferable from the standpoint of full-color image quality to improve clarity.

[0094] The following are examples of pigments used for magenta toner: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0095] Examples of dyes for magenta toner include: oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0096] Examples of pigments for cyan toner include: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Bat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which phthalimidomethyl groups are substituted onto the phthalocyanine skeleton.

[0097] CI Solvent Blue 70 is a dye used for cyan toner.

[0098] The following pigments are used for yellow toner: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20. CI Solvent Yellow 162 is a dye used for yellow toner.

[0099] These colorants can be used individually, in combination, or even in solid solution form. The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner.

[0100] The coloring agent content is preferably 0.1 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of the binder resin.

[0101] <Charge control agent> Toner particles may contain a charge control agent as needed. By incorporating a charge control agent, the charge characteristics are stabilized, allowing for optimal control of the amount of triboelectric charge according to the developing system.

[0102] While known charge control agents can be used, aromatic carboxylic acid metal compounds are particularly preferred because they are colorless, have a fast toner charging speed, and can stably maintain a constant charge level.

[0103] Examples of negative charge control agents include salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid as a side chain, polymer compounds having sulfonate salts or sulfonic acid esters as a side chain, polymer compounds having carboxylate salts or carboxylic acid esters as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0104] The charge control agent may be added internally or externally to the toner particles. When added internally, the content of the charge control agent is preferably 0.2 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, per 100 parts by mass of the binder resin.

[0105] <Developer> The toner of the present invention can be used as a one-component developer, but it is more preferable to use it as a two-component developer mixed with a magnetic carrier, as this provides stable images over a long period of time.

[0106] As magnetic carriers, generally known materials can be used, such as iron powder with an oxidized surface, or iron powder without oxidation, or magnetic materials such as metal particles like iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, and rare earth elements, or their alloy particles, oxide particles, or ferrite, or magnetic material dispersion resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0107] When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the toner and carrier is preferably 2.0% by mass or more and 15.0% by mass or less, and more preferably 4.0% by mass or more and 13.0% by mass or less, in terms of toner concentration.

[0108] <Toner manufacturing method> The manufacturing method of the toner of the present invention is not particularly limited, but a manufacturing method suitable for producing the toner of the present invention will be described in detail.

[0109] A suitable manufacturing method for producing the toner of the present invention is the kneading and grinding method. The kneading and grinding method is a toner manufacturing method comprising a melting and kneading step to obtain a molten kneaded product by melting and kneading a toner composition containing a binder resin and a release agent, etc., and a grinding step to obtain a pulverized product by cooling and solidifying the molten kneaded product and grinding the cooled and solidified product.

[0110] With the above manufacturing method, by melt-kneading a mixture in which the ratio of crystalline resin to amorphous resin is controlled, it is possible to obtain a matrix-domain structure composed of a matrix containing crystalline resin and domains containing amorphous resin.

[0111] The following describes the toner manufacturing procedure using the melt-kneading and grinding method.

[0112] [Raw material mixing process] In the raw material mixing process, predetermined amounts of materials that constitute toner particles, such as binder resin, wax, colorant, and other components such as charge control agents as needed, are weighed, blended, and mixed. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0113] [Melting and mixing process] Next, the mixed materials are melt-kneaded to disperse wax and other substances into the binder resin. In this melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, or continuous kneaders can be used, and single-screw or twin-screw extruders are the mainstream due to their advantage of being able to produce continuously. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works, Ltd.), the twin-screw extruder (manufactured by KCK Co., Ltd.), the Co-kneader (manufactured by Buss Co., Ltd.), and the Nidex (manufactured by Nippon Coke Industries, Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water in a cooling process.

[0114] Examples of methods for rolling a resin composition include rolling it with twin-screw rollers or a drum and then cooling it with a steel belt cooler (manufactured by Nippon Steel Conveyor Co., Ltd.), or rolling it while cooling it with a press roller and a drum equipped with an internal cooling mechanism, such as a belt drum flaker (manufactured by Nippon Coke Co., Ltd.).

[0115] By controlling the mixing temperature and screw rotation speed during the melt-mixing process, it is possible to control the dispersion state of crystalline resin and amorphous resin, as well as the average number diameter of domains.

[0116] [Grinding process] Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, for example, it is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Cryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industries Co., Ltd.), or an air jet type pulverizer.

[0117] [Classification process] Subsequently, the materials are classified as needed using classifiers or sieves such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), and the Faculty (manufactured by Hosokawa Micron Corporation).

[0118] [External addition process] Furthermore, an external additive is applied to the surface of the toner particles. Methods for applying the external additive include mixing a predetermined amount of classified toner particles, organosilicon polymer particles, and various known external additives, and then stirring and mixing them using a mixing device such as a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), or Novilta (manufactured by Hosokawa Micron Corporation) as the external additive machine.

[0119] The following describes methods for measuring various physical properties related to the toner of the present invention.

[0120] <Cross-sectional observation of toner particles, measurement of matrix domain structure> First, a thin section is prepared to serve as a reference sample for the amount of the substance present.

[0121] Crystalline resin is thoroughly dispersed in a visible light-curable resin (Arronix LCR series D800), and then cured by irradiation with short-wavelength light. The resulting cured material is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin-section samples. Thin-section samples are prepared in the same manner for amorphous resins.

[0122] Furthermore, crystalline resin and amorphous resin are mixed by mass in ratios of 0 / 100, 30 / 70, 70 / 30, and 0 / 100 to prepare a compound by melt-kneading. These are also dispersed in a visible light-curable resin, cured, and then cut to produce thin flake samples.

[0123] Next, the cut samples are observed in cross-section using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX), and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen. The mapping conditions are as follows: Acceleration voltage: 200kV Electron beam irradiation size: 1.5 nm Live time limit: 600 sec Dead time: 20-30 Mapping resolution: 256×256

[0124] Based on the average spectral intensity of each element (over a 10 nm square area), the (oxygen intensity / carbon intensity) and (nitrogen intensity / carbon intensity) ratios are calculated, and a calibration curve is created for the mass ratio of crystalline resin to amorphous resin. If nitrogen atoms are present in the monomer units of the crystalline resin, the (nitrogen intensity / carbon intensity) calibration curve will be used for future quantification.

[0125] Next, we will analyze the toner sample.

[0126] After thoroughly dispersing toner in a visible light-curable resin (Arronix LCR series D800), the resin is cured by irradiation with short-wavelength light. The resulting cured material is then cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin-section samples.

[0127] Next, the excised sample is observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX). Cross-sectional images of the toner particles are obtained, and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.

[0128] The toner particle cross-sections to be observed are selected as follows: First, the cross-sectional area of ​​the toner particle is determined from the toner particle cross-sectional image, and the diameter of a circle with an area equal to that cross-sectional area (equivalent circle diameter) is determined. Only toner particle cross-sectional images where the absolute value of the difference between this equivalent circle diameter and the weight-average particle size (D4) of the toner is 1.0 μm or less are observed.

[0129] For the domains identified by the observation image, the ratio of crystalline resin to amorphous resin is calculated by determining the (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) based on the (average 10 nm square) spectral intensity of each element, and comparing these with the calibration curve. Domains in which the amorphous resin ratio is 80% or more are defined as "amorphous resin domains" in this disclosure.

[0130] After identifying the domains confirmed by the observation image, the particle size of the domains present in the toner cross-sectional image is determined by binarization. The particle size is defined as the major axis of the domain. Ten measurements are taken for each toner particle, and the arithmetic mean of the domain particle sizes of 10 toner particles is taken as the number-average diameter of the domains (μm).

[0131] Image Pro PLUS (manufactured by Roper Japan Co., Ltd.) was used for binarization and calculation of the average diameter.

[0132] <Method for separating each material from toner> By utilizing the differences in the solubility of each material contained in the toner in the solvent, it is possible to separate the materials from the toner. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C to separate the soluble components (amorphous resin) from the insoluble components (crystalline resin, wax, colorants, external additives, etc.). Second separation: The insoluble components (crystalline resin, wax, colorants, external additives, etc.) obtained in the first separation are dissolved in MEK at 100°C, and the soluble components (crystalline resin, wax) and insoluble components (colorants, external additives, etc.) are separated. Third separation: The soluble components (crystalline resin, wax) obtained in the second separation are dissolved in chloroform at 23°C, and the soluble components (crystalline resin) and insoluble components (wax) are separated.

[0133] <Separation of external additives and toner particles> Add 200g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it over a water bath to prepare a concentrated sucrose solution. Place 31g of this concentrated sucrose solution and 6mL of Contaminon N (a 10% by mass 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.) into a centrifuge tube to prepare a dispersion. Add 1g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0134] The centrifugation tube is shaken for 20 minutes at a rate of 350 strokes per minute using a shaker (Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX)). After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL), and centrifugation is performed in a centrifuge at 3500 rpm for 30 minutes.

[0135] After centrifugation, toner particles are present in the uppermost layer of the glass tube, while external additive particles (organosilicon polymers, inorganic microparticles, etc.) are present in the lower aqueous solution layer. The lower aqueous solution is collected and centrifuged to separate the sucrose from the external additive particles, and the external additive is collected. Centrifugation may be repeated as needed. If multiple types of external additives are added, each external additive can be separated by adjusting the centrifugation conditions.

[0136] (Measurement of the content of crystalline resin and amorphous resin in the binder resin of toner) In each separation step obtained through the above separation process, the mass of soluble and insoluble components is measured to calculate the content of crystalline resin and amorphous resin in the binder resin of the toner.

[0137] <Method for identifying monomer units constituting the first, second, and third resins and measuring their content ratio> The identification and measurement of the content ratio of monomer units constituting the first, second, and third resins are as follows: 1 The procedure is performed using H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0138] obtained 1 In the 1H-NMR chart, a peak independent of the peaks assigned to the components of the other monomer units is selected from among the peaks assigned to the components of the first monomer unit, and the integral value S1 of this peak is calculated.

[0139] Similarly, from among the peaks attributed to the components of the second monomer unit, a peak independent of the peaks attributed to the components of other monomer units is selected, and the integral value S2 of this peak is calculated.

[0140] Furthermore, if a third monomer unit is present, a peak independent of the peaks attributed to the components of the other monomer units is selected from the peaks attributed to the components of the third monomer unit, and the integral value S3 of this peak is calculated.

[0141] The content of the first monomer unit is determined using the integral values ​​S1, S2, and S3 as follows. Note that n1, n2, and n3 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part. Content percentage (mol%) of the first monomer unit = {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100

[0142] Similarly, the content ratios of the second and third monomer units are determined as follows. Second monomer unit content (mol%) = {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 The content percentage (mol%) of the third monomer unit = {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100

[0143] Furthermore, in the first, second, and third resins, if, for example, polymerizable monomers in which hydrogen atoms are not included in components other than vinyl groups are used, 13 Using 13C NMR, the measurement nucleus was set to 13C, and the measurement was performed in single-pulse mode. 1 The calculation is performed in the same manner as with H-NMR.

[0144] Based on the molecular weight of the monomer unit, the percentage can be converted from mol% to mass%.

[0145] <Method for measuring the melting point, endothermic peak, and endothermic amount of toner and resin, etc.> The melting points of toners and resins, as well as the endothermic peaks and endothermic amounts, are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃ The temperature correction for the device's detection unit uses the melting points of indium and zinc, while the heat of fusion of indium is used for heat quantity correction.

[0146] Specifically, approximately 5 mg of the sample is accurately weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference.

[0147] The peak temperature of the maximum endothermic peak during the first heating process is defined as the melting point.

[0148] The maximum endothermic peak is the peak with the largest amount of heat absorbed when there are multiple peaks. Furthermore, the amount of heat absorbed at the maximum endothermic peak is determined.

[0149] Furthermore, the tetrahydrofuran (THF) insoluble portion of the toner, after removing the inorganic components, should be prepared as described below.

[0150] <Method for measuring the softening point (Tm) of resin> The softening point of the resin is measured using a constant-load extrusion type capillary rheometer, the "Flow Characteristics Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation), according to the manual included with the device. With this device, a constant load is applied from the top of the sample by a piston, the sample filled in the cylinder is heated and melted, and the molten sample is extruded from a die at the bottom of the cylinder. A flow curve showing the relationship between the piston descent amount and temperature can be obtained.

[0151] Furthermore, the softening point will be the "melting temperature using the 1 / 2 method" as described in the manual included with the "Flow Characteristics Evaluation Device Flow Tester CFT-500D". The melting temperature using the 1 / 2 method is calculated as follows:

[0152] First, we calculate half the difference between the piston's descent at the end of the outflow (the end of the outflow, let's call it Smax) and the piston's descent at the start of the outflow (the lowest point, let's call it Smin) (let's call this X; X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston's descent is the sum of X and Smin is the melting temperature using the 1 / 2 method.

[0153] The sample used for measurement is a cylindrical shape with a diameter of approximately 8 mm, prepared by compressing approximately 1.0 g of resin at approximately 10 MPa for approximately 60 seconds in a tablet molding compressor (e.g., NT-100H, manufactured by NPA System Co., Ltd.) at a temperature of 25°C.

[0154] Specific procedures for measurement should be followed according to the manual provided with the device.

[0155] The measurement conditions for the CFT-500D are as follows: Test mode: Temperature increase method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1,000 cm² 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheating time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0156] <Method for measuring the weight-average particle size (D4) of toner particles> The weight-average particle size (D4) of toner (particles) is measured using the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data, with an effective measurement channel count of 25,000. The measurement data is then analyzed and calculated.

[0157] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0158] Before performing measurements and analysis, configure the dedicated software as follows.

[0159] In the dedicated software's "Change Standard Measurement Method (SOM)" screen, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the Threshold / Noise Level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the box for flushing the aperture tube after measurement.

[0160] In the dedicated software's "Pulse to Particle Size Conversion Settings Screen," set the bin spacing to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0161] The specific measurement method is as follows: (1) Place approximately 200 mL of electrolytic solution into a 250 mL round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tubes. (2) Place approximately 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottomed glass beaker, and add approximately 0.3 mL of a diluted solution of "Contaminon N" (a 10% by mass 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.) diluted three times by mass with deionized water as a dispersant. (3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase difference of 180 degrees, and a predetermined amount of deionized water is placed in the water tank of an ultrasonic dispersion device called "Ultrasonic Dispersion System Tetora150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120 W, and approximately 2 mL of Contaminon N is added to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add approximately 10 mg of toner (particles) to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank as appropriate so that it is between 10°C and 40°C. (6) Using a pipette, the electrolytic aqueous solution from (5) containing dispersed toner (particles) is dropped into the round-bottom beaker from (1) placed in the sample stand, and the concentration is adjusted to approximately 5%. The measurement is then continued until the number of particles to be measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that the "Average Diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen when the dedicated software is set to Graph / Volume % is the weight-average particle size (D4).

[0162] <Measurement of average circularity> The average circularity of the toner is measured using the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions used during calibration.

[0163] The specific measurement method is as follows:

[0164] First, put about 20 mL of deionized water, from which impurities and other solids have been removed, into a glass container. Add about 0.2 mL of a diluted solution of "Contaminon N" (a 10% by mass 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.) diluted with deionized water to about 3 times its original volume as a dispersant.

[0165] Furthermore, approximately 0.02 g of the sample to be measured is added and dispersed for 2 minutes using an ultrasonic disperser to prepare the dispersion for measurement. During this process, the dispersion is cooled as needed so that its temperature is between 10°C and 40°C. A tabletop ultrasonic cleaner disperser ("VS-150" (manufactured by Velvo-Clear Co., Ltd.)) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used as the ultrasonic disperser. A predetermined amount of deionized water is placed in the water tank, and approximately 2 mL of the aforementioned Contaminon N is added to this water tank.

[0166] For the measurement, the flow-type particle image analyzer equipped with a standard objective lens (10x) was used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure was introduced into the flow-type particle image analyzer, and 3000 toner particles were measured in HPF measurement mode and total count mode.

[0167] Then, the binarization threshold for particle analysis is set to 85%, and the analyzed particle diameter is limited to a circular equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner is determined.

[0168] Before starting the measurement, autofocus adjustment should be performed using standard latex particles (Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" diluted with deionized water). Subsequently, it is preferable to perform focus adjustment every two hours from the start of the measurement.

[0169] In this example, a flow-type particle image analyzer that had been calibrated by Sysmex Corporation and for which a calibration certificate was issued by Sysmex Corporation was used. Except for limiting the analyzed particle size to a circular equivalent diameter of 1.985 μm or more and less than 39.69 μm, measurements were performed under the measurement and analysis conditions at the time the calibration certificate was issued.

[0170] <Method for measuring the Young's modulus of organosilicon polymer particles and toner> The Young's modulus of organosilicon polymer particles and toner is determined from microcompression tests using a Hyditron PI 85L picoindenter (BRUKER) at 25°C. The Young's modulus (MPa) is calculated from the slope of the profile (stress-strain curve) obtained from the displacement (nm) and test force (μN) obtained from the measurement. • Equipment and jigs Base system: Hysitron PI-85L Measuring indenter: Flat-end indenter with a circular tip with a diameter of 1 μm. SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV • Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / second Hold time: 2 seconds Unloading speed: 5nm / sec ·Analysis method Hertz analysis is applied to the obtained load-displacement curves for compression from 0 nm to 10 nm to calculate the Young's modulus of each particle. • Sample adjustment Organic silicon polymer particles: Use those with organic silicon polymer particles attached on a silicon wafer. Toner: Weigh 0.1 g of the toner, and under the environment of room temperature (25 °C), use a tablet molding machine to form a pellet with a diameter of 8.0 mm and a thickness of 1.5 ± 0.3 mm into a disc shape as a test piece.

[0171] <Measurement method of XRD (X-ray diffraction)> For XRD, use the measuring device "RINT-TTRII" (manufactured by Rigaku Corporation), and the control software and analysis software attached to the device.

[0172] The measurement conditions are as follows. X-ray: Cu / 50 kV / 300 mA Goniometer: Rotor horizontal goniometer (TTR-2) Attachment: Standard sample holder Divergence slit: Open Divergence vertical limit slit: 10.00 mm Scattering slit: Open Receiving slit: Open Counter: Scintillation counter Scanning mode: Continuous Scan speed: 4.0000 ° / min. Sampling width: 0.0200 ° Scanning axis: 2θ / θ Scanning range: 10.0000 to 40.0000 °

[0173] Subsequently, set the toner on the sample plate and start the measurement. In the CuKα characteristic X-ray, perform the measurement in the range of diffraction angle 2θ (2θ ± 0.20 deg) 3 deg to 35 deg, and use the spectrum at 2θ of 20.0 deg to 23.0 deg from the obtained spectrum as an index of crystallinity in the toner.

[0174] <Solid 29 <Measurement method of the abundance ratio of organic silicon polymer particles by solid Si-NMR> Solid 29In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional groups bonded to Si in the constituent compounds of organosilicon polymer particles.

[0175] The structure bonded to Si can be identified by determining the position of each peak using a standard sample. Furthermore, the relative abundance of each constituent compound can be calculated from the obtained peak areas. The ratio of the peak areas of the Q unit structure, T unit structure, and D unit structure to the total peak area can be calculated. solid 29 The specific measurement conditions for Si-NMR are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29Si 45° Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 10kHz Relaxation delay: 180s Scan: 2000

[0176] After the measurement, the silane components of the sample or organosilicon polymer particles with different substituents and bonding groups are separated into peaks for the following M, D, T, and Q unit structures by curve fitting, and the peak area of ​​each is calculated.

[0177] [ka] Let (S1+S2+S3+S4)=SA.

[0178] In the above formulas (S1), (S2), and (S3), R represents a hydrocarbon group having 1 to 6 carbon atoms. If further structural details need to be confirmed, see above. 13 C-NMR and 29 Along with the Si-NMR measurement results 1 Identification may also be performed based on the results of 1H-NMR measurements.

[0179] From SA, S2, S3, and S4 obtained in this way, S2 / SA, S3 / SA, and S4 / SA are calculated.

[0180] [Configurations included in embodiments of the present invention] This embodiment includes the following configuration. (Configuration 1) A toner having toner particles containing a binder resin, and organosilicon polymer particles on the surface of the toner particles, The binder resin contains a crystalline resin, When the Young's modulus of a test piece obtained by pelletizing the toner is measured at 25°C using a microcompression tester and the Young's modulus of one particle of the organosilicon polymer separated from the toner is measured at 25°C using a microcompression tester and the Young's modulus of that particle is measured at 25°C using a microcompression tester, then the TE and the SiE are, 800 ≤ TE ≤ 2500 1.5 ≤ SiE / TE ≤ 10.0 A toner characterized by satisfying the following conditions. (Configuration 2) The toner according to Configuration 1, wherein the content of the crystalline resin is 50% by mass or more, based on the binder resin. (Configuration 3) The toner according to Configuration 1 or 2, wherein the content of the organosilicon polymer particles is 0.5 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of toner particles. (Configuration 4) The toner is the toner according to any one of Configurations 1 to 3, having diffraction peaks in the range of diffraction angle 2θ of 20.0° or more and 22.0° or less in an X-ray diffraction spectrum using CuKα rays. (Configuration 5) The crystalline resin has monomer units represented by the above formula (1), The toner according to any one of configurations 1 to 4, wherein the proportion of the monomer unit is 30.0% by mass or more, based on the mass of the crystalline resin. (Configuration 6) The toner particles contain an amorphous resin, When the cross-section of the toner particles was observed using a transmission electron microscope, amorphous resin domains were observed in the cross-section. The toner according to any one of configurations 1 to 5, wherein, in the cross-section, the number-average particle size of the domains located within 800 nm from the surface of the toner particles is 20 nm or more and 500 nm or less. (Configuration 7) The organosilicon polymer particles are used as a sample. 29 In Si-NMR measurements, when the total peak area originating from the organosilicon polymer is denoted as SA, the peak area originating from Q units as S4, the peak area originating from T units as S3, and the peak area originating from D units as S2, 0.20 ≤ S4 / SA ≤ 0.60 0.00 ≤ S3 / SA ≤ 0.50 0.20 ≤ S² / SA ≤ 0.70 A toner described in any of configurations 1 to 6 that satisfies the requirements. (Configuration 8) The toner according to any of Configurations 1 to 7, wherein the average circularity of the toner is 0.930 or more and 0.980 or less. [Examples]

[0181] The basic structure and features of the present invention have been described above. The present invention will now be described in detail based on examples. However, the present invention is not limited thereto. Unless otherwise specified, parts are measured by mass.

[0182] <Example of manufacturing crystalline resin 1> • Solvent: Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, acrylonitrile, and styrene in the proportions shown below.) Behenyl acrylate 60.0 parts • Acrylonitrile 10.0 parts (30.0 parts of styrene) • Polymerization initiator 0.5 part [t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)] The above materials were placed in a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene.

[0183] Next, the above solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain crystalline resin 1. The melting point (Tp) of crystalline resin 1 was 61°C.

[0184] <Examples of manufacturing crystalline resins 2-10> In the example of producing crystalline resin 1, the reaction was carried out in the same manner except that the monomers and parts by mass of each component were changed to those shown in Table 1, and crystalline resins 2 to 10 were obtained.

[0185] [Table 1] The abbreviations used in Table 1 are as follows: BEA: Behenyl Acrylate STA: Stearyl Acrylate MYA: Myricyl Acrylate HA: Hexadecyl acrylate AN: Acrylonitrile St: Styrene

[0186] <Example of manufacturing crystalline resin 11> · 1,12-Dodecanediol: 46.5 parts Dodecanediol: 53.3 parts • Tin 2-ethylhexanoate: 0.5 parts The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was carried out for 3 hours at a temperature of 140°C while stirring.

[0187] Next, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C.

[0188] Subsequently, the reaction vessel was subjected to a reduced pressure of 5 kPa or less and reacted at 200°C for 3 hours to obtain crystalline resin 11.

[0189] <Example of Amorphous Resin 1 Production> 50.0 parts xylene was placed in an autoclave, the water was purged with nitrogen, and the temperature was raised to 185°C under stirring and in a sealed state.

[0190] A mixed solution of 80.7 parts styrene, 17.8 parts n-butyl acrylate, 1.1 parts divinylbenzene, 0.5 parts acrylic acid, 1.5 parts di-tert-butyl peroxide, and 20.0 parts xylene was added dropwise for 3 hours while controlling the autoclave temperature to 185°C, and polymerization was carried out.

[0191] The mixture was then maintained at the same temperature for 1 hour to complete polymerization, and the solvent was removed to obtain amorphous resin 1. The softening point (Tm) of amorphous resin 1 was 100°C.

[0192] <Example of Amorphous Resin 2 Production> (Formulation of polyester resin components) • Bisphenol A ethylene oxide (2.2 mol adduct) 50.0 mol parts • Bisphenol A propylene oxide (2.2 mol adduct) 50.0 mol parts Terephthalic acid 65.0 mol • Trimellitus anhydride 25.0 mol 10.0 mol parts of acrylic acid Ninety parts of the monomer mixture used to produce the polyester resin component were placed in a four-necked flask, and the flask was stirred at 160°C under a nitrogen atmosphere with a vacuum device, water separator, nitrogen gas introduction device, temperature measuring device, and stirring device attached.

[0193] There, 10 parts of a vinyl-based polymerizable monomer (81.0 parts of styrene, 17.0 parts of n-butyl acrylate, 0.9 parts of acrylic acid, 1.1 parts of divinylbenzene) that produces a vinyl-based resin component and 1 part of benzoyl peroxide as a polymerization initiator were dropped from a dropping funnel over 4 hours and reacted at 160 °C for 5 hours.

[0194] Thereafter, the temperature was raised to 230 °C, 0.2 parts of titanium tetrabutoxide was added with respect to the total amount of the monomers that produce the polyester resin component, and polymerization was carried out until the softening point (Tm) reached 115 °C.

[0195] After completion of the reaction, it was taken out from the container, cooled, and pulverized to obtain amorphous resin 2.

[0196] <Production Example of Toner Particles 1> In this production example, toner particles were produced using an emulsion polymerization method. First, each dispersion was produced by the method described below.

[0197] [Production of Crystalline Resin 1 Fine Particle Dispersion] · 300 parts of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) · 100 parts of crystalline resin 1 The above materials were weighed and mixed, and dissolved at 100 °C.

[0198] Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water and heated and dissolved at 100 °C. Next, the toluene solution and the aqueous solution were mixed and stirred at 7000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (crystalline resin 1 fine particle dispersion) having a concentration of 20% by mass of crystalline resin 1 fine particles.

[0199] When the volume-based 50% particle size (D50) of the crystalline resin 1 was measured using a dynamic light scattering particle size distribution analyzer NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.40 μm.

[0200] [Production of amorphous resin 1 fine particle dispersion] · 300 parts of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) · 100 parts of amorphous resin 1 · 0.5 part of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) The above materials were weighed, mixed, and dissolved.

[0201] Next, 20.0 parts of 1 mol / L aqueous ammonia was added, and the mixture was stirred at 4000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Further, 700 parts of ion-exchanged water was added at a rate of 8 g / min to precipitate the amorphous resin 1 fine particles. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (amorphous resin 1 fine particle dispersion) having a concentration of 20% by mass of amorphous resin 1 fine particles.

[0202] The volume-based 50% particle size (D50) of the amorphous resin 1 fine particles was 0.14 μm.

[0203] [Production of wax fine particle dispersion] · 100.0 parts of wax 1 (Fisher-Tropsch wax; peak temperature of the maximum endothermic peak: 90 °C) · 5 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) · 395 parts of ion-exchanged water The above materials were weighed and put into a mixing container equipped with a stirrer. After heating to 90 °C, the mixture was circulated through a ClearMix W motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for the dispersion treatment were as follows. · Outer diameter of rotor: 3 cm · Clearance: 0.3 mm · Rotor rotation speed: 19000 r / min Screen rotation speed: 19000 r / min After dispersion treatment, the mixture was cooled to 40°C under cooling conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10°C / min to obtain an aqueous dispersion of wax fine particles with a concentration of 20% by mass (wax fine particle dispersion).

[0204] The 50% volume-based particle size (D50) of wax microparticles was measured using a dynamic light scattering particle size analyzer, NanoTrac UPA-EX150 (manufactured by Nikkiso), and was found to be 0.15 μm.

[0205] [Manufacturing of colorant particle dispersion] • Coloring agent 1 50.0 parts (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15:3) • Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 7.5 parts • Ion-exchanged water 442.5 parts The above materials were weighed, mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Machinery Industry Co., Ltd.) to obtain an aqueous dispersion of colorant fine particles with a concentration of 10% by mass (colorant fine particle dispersion).

[0206] The 50% volume-based particle size (D50) of the colorant microparticles was measured using a dynamic light scattering particle size analyzer, NanoTrac UPA-EX150 (manufactured by Nikkiso), and was found to be 0.20 μm.

[0207] Toner particles were produced using the dispersions manufactured by the above method, according to the following procedure.

[0208] [Manufacturing of toner particles 1] ·Crystalline resin 1 fine particle dispersion 60.0 parts ·Amorphous resin 1 fine particle dispersion liquid 40.0 parts • Wax particle dispersion 5.0 parts • Colorant fine particle dispersion 9.0 parts • Ion-exchanged water 20.0 parts • 3.0 parts of a dispersion of crystalline resin microparticles for post-treatment. Each material other than the above-mentioned crystalline resin 1 fine particle dispersion for post-treatment was put into a round stainless steel flask and mixed. Subsequently, it was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra-Turrax T50 (manufactured by IKA). After adding a 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, it was heated to 58 °C in a water bath for heating while appropriately adjusting the rotation speed such that the mixed solution was stirred using a stirring blade. The formed aggregated particles were appropriately confirmed using a Coulter Multisizer III and maintained until the weight average particle diameter (D4) reached approximately 6.4 μm. Thereafter, the crystalline resin 1 fine particle dispersion for post-treatment was added, and after further holding for 30 minutes, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution.

[0209] Thereafter, while continuing stirring, it was heated to 75 °C. Then, the aggregated particles were fused by holding at 75 °C for 1 hour.

[0210] Thereafter, it was cooled to 50 °C and held for 3 hours to promote the crystallization of the resin.

[0211] Thereafter, it was cooled to 25 °C, filtered and solid-liquid separated, thoroughly washed with ion-exchanged water, and dried to obtain toner particles 1. The weight average particle diameter (D4) of the toner particles 1 was approximately 6.0 μm, the average circularity was 0.975, and the domain diameter was 200 nm.

[0212] <Production Example of Toner Particles 2> In this production example, toner particles were produced using the melt-kneading and pulverization method. · Crystalline resin 1 60.0 parts · Amorphous resin 1 40.0 parts · Wax 1 5.0 parts (Fisher-Tropsch wax; melting point 90 °C) · Colorant 1 9.0 parts (Cyan pigment manufactured by Dainichi Seika: Pigment Blue 15:3) The above materials were used with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.) at a rotation speed of 20 s -1After mixing for 5 minutes, the mixture was kneaded in a twin-screw mixer (PCM-30 model, manufactured by Ikegai Co., Ltd.) with a screw rotation speed of 250 rpm and a discharge temperature of 130°C. The resulting mixture was rolled and cooled in a drum flaker (MBD30-30, manufactured by Nippon Coke Co., Ltd.). The cooling water temperature was set to 15°C, and the conditions were set so that the thickness of the resin composition after rolling and cooling was 1.0 mm. The temperature from melting to below the melting point Tp of the crystalline resin was (10 seconds), and the cooling rate from rolling to below the melting point Tp of the crystalline resin was (7°C / second). The mixture was coarsely ground to a size of 1 mm or less in a hammer mill to obtain coarse material. The obtained coarse material was finely ground in a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.).

[0213] Furthermore, classification was performed using a Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 2 with a weight-average particle size of approximately 6.0 μm, an average circularity of 0.965, and a domain diameter of 200 nm. The classification operating conditions were a classification rotor rotation speed of 130 s. -1 , the distributed rotor rotation speed is 120s -1 That's what I decided.

[0214] <Manufacturing example of toner particles 3-24> In the example of toner particle 2 manufacturing, the type and amount of crystalline resin added, and the type and amount of amorphous resin added. Except for the changes in the number of units added and the mixing conditions as shown in Table 2, the manufacturing process was carried out in the same manner, and the toner was used. Particles 3-24 were obtained.

[0215] [Table 2] *Toner particles 1 are produced by emulsification and coagulation, therefore no kneading conditions are required.

[0216] <Example of production of organosilicon polymer particles 1> 1. Hydrolysis process: In a 200 ml beaker, 43.2 parts of RO water and 0.008 parts of acetic acid as a catalyst were charged and stirred at 45°C. 27.2 g of tetraethoxysilane and 27.2 parts of dimethyldimethoxysilane were added and stirred for 1.5 hours to obtain the raw material solution.

[0217] 2. Polycondensation process: In a 1000 ml beaker, 68.8 parts RO water, 340.0 parts methanol, and 2.0 parts 25% aqueous ammonia were added and stirred at 30°C to prepare an alkaline aqueous medium. To this alkaline aqueous medium, the raw material solution obtained in the above hydrolysis step was added dropwise over 1 minute. The mixture after the addition of the raw material solution was stirred at 30°C for 1.5 hours to allow the polycondensation reaction to proceed and obtain a polycondensation reaction solution.

[0218] 3.Particleization process: 1000 parts of RO water were added to a 2000 ml beaker, and the polycondensation reaction solution obtained in the above condensation polymerization step was added dropwise over 10 minutes while stirring at 25°C. As soon as the polycondensation reaction solution mixed with water, it became cloudy, and a dispersion containing silicon polymer particles having siloxane bonds was obtained.

[0219] 4. Hydrophobization process: To a dispersion containing silicon polymer particles having siloxane bonds obtained in the above particle formation process, 27.1 parts of hexamethyldisilazane were added as a hydrophobic agent, and the mixture was stirred at 60°C for 2.5 hours. After standing for 5 minutes, the powder that settled at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain organosilicon polymer particles 1. The Young's modulus of the primary particle size of the obtained organosilicon polymer 1 particles was 6200 MPa. The physical properties of organosilicon polymer particles 1, which are an external additive for toner, are shown in Table 3.

[0220] <Examples of manufacturing organosilicon polymer particles 2-11> In the example of producing organosilicon polymer particles 1, the production was carried out in the same manner except that the composition of the added monomers in the hydrolysis step was changed as shown in Table 3, and organosilicon polymer particles 2 to 11 were obtained.

[0221] [Table 3]

[0222] <Example of Toner 1 manufacturing> • Toner particles 1 100 copies • Organosilicon polymer particles 1 5.0 parts The above ingredients were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Machinery) at a rotation speed of 30 seconds. -1 The mixture was rotated for 10 minutes to obtain toner 1. The obtained toner was pelletized and measured to have a Young's modulus of 1700 MPa.

[0223] <Manufacturing examples for toners 2-35> In the manufacturing example of Toner 1, the same procedure was followed except that the types and quantities of toner particles and organosilicon polymer particles were changed to those listed in Table 4, thereby obtaining Toners 2 to 35. For Toner 35, 5.0 parts of silica fine particles (number-average particle size 120 nm, Young's modulus 71000 MPa) were used instead of organosilicon polymer particles.

[0224] [Table 4]

[0225] <Manufacturing example of magnetic carrier 1> • Number-average particle size 0.30 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 1 ( / kg) • Number-average particle size 0.50 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 2 ( / kg) To each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was rapidly mixed and stirred in a container at over 100°C to treat the respective fine particles. • Phenolic: 10% by mass Formaldehyde solution: 6% by mass (40% formaldehyde by mass, 10% methanol by mass, 50% water by mass) • Magnetite treated with the above silane compound 1:58 mass% • Magnetite treated with the above silane compound: 2:26% by mass 100 parts of the above material, 5 parts of a 28% by mass ammonia aqueous solution, and 20 parts of water were placed in a flask, and while stirring and mixing, the temperature was raised to 85°C for 30 minutes and maintained there, and the polymerization reaction was carried out for 3 hours to cure the resulting phenolic resin.

[0226] The cured phenolic resin was then cooled to 30°C, water was added, the supernatant was removed, the precipitate was washed with water, and then it was air-dried.

[0227] Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain spherical magnetic carriers 1 in the form of magnetic material dispersion. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0228] <Example of manufacturing a two-component developer 1> 92.0 parts of magnetic carrier 1 were mixed with 8.0 parts of toner 1 using a V-type mixer (V-20, manufactured by Seishin Corporation) to obtain a two-component developer 1.

[0229] <Manufacturing examples of two-component developers 2-35> In the example of manufacturing two-component developer 1, the manufacturing process was carried out in the same manner except that the toner was changed as shown in Table 5, to obtain two-component developers 2 to 35.

[0230] [Example 1] The evaluation was performed using the two-component developer 1 described above.

[0231] [Low temperature fixation] As the image forming apparatus, a modified Canon imageRUNNER ADVANCE C5560 digital commercial printer with an intermediate transfer body was used, and a two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included allowing free setting of the fixing temperature, process speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. For image output evaluation, a solid-tone image (FFh image) with the desired image ratio was output, and the VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image on the paper was as desired, and the low-temperature fixing performance was evaluated.

[0232] FFh is a hexadecimal value representing 256 gradations, where 00h is the first gradation (white area) of the 256 gradations, and FFh is the 256th gradation (solid area).

[0233] The evaluation was conducted based on the following evaluation method, and the results are shown in Table 5. ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.70 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper shown above. • Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 400 mm / sec The above evaluation images were output, and the low-temperature fixability was assessed. The value of the image density reduction rate was used as the evaluation index for low-temperature fixability.

[0234] The image density reduction rate is determined using an X-Rite color reflectance densitometer (500 series: manufactured by X-Rite). First, the image density in the central area is measured. Next, a load of 4.9 kPa (50 g / cm2) is applied to the area where the image density was measured, and the fixed image is rubbed with lens tissue (5 back-and-forth motions), and the image density is measured again.

[0235] The percentage decrease in image density before and after friction was calculated using the following formula. The obtained percentage decrease in image density was evaluated according to the evaluation criteria below. The evaluation results are shown in Table 5. Image density reduction rate = (Image density before friction - Image density after friction) / (Image density before friction) × 100

[0236] (Evaluation Criteria) AA: Image density reduction rate less than 1.0% A: Image density reduction rate less than 3.0% B: Image density reduction rate of 3.0% or more and less than 5.0% C: Image density reduction rate of 5.0% or more and less than 8.0% D: Image density decrease rate of 8.0% or more

[0237] [Transferability (non-electrostatic adhesion)] A modified Canon imageRUNNER ADVANCE C5255 full-color copier with an intermediate transfer element was used as the image forming apparatus. Solid images were output under normal temperature and humidity conditions (temperature 23°C, relative humidity 50%).

[0238] The residual toner on the photoreceptor drum during solid image formation was taped off using transparent polyester adhesive tape. The removed adhesive tape was then placed on paper, and its density was measured using a 500 series spectrophotometer (X-Rite). Additionally, the density of the adhesive tape alone was also measured. The density difference was calculated by subtracting the latter density from the former density, and this density difference was evaluated based on the evaluation criteria shown below. The initial non-electrostatic adhesion evaluation results are shown in Table 5.

[0239] The evaluation paper used was multi-purpose copy paper, commonly known as voice paper (A4 size, 75g / m² basis weight). 2 (Sold by Canon USA) was used. A score of C or higher was judged to indicate that the effects of the present invention were obtained.

[0240] (Criteria for evaluating transcriptional properties) A: Concentration difference less than 0.05 B: Concentration difference 0.05 or more and less than 0.10 C: Concentration difference between 0.10 and less than 0.20 D: Density difference 0.20 or more

[0241] Next, using an image with a print ratio of 1%, the toner was quantitatively replenished to maintain a constant density, and 70,000 images (70k) were printed. The image output paper was CS-680 (A4, basis weight 68g / m²). 2 (Sold by Canon Marketing Japan Inc.)

[0242] After the 70k durability test, the transferability was evaluated using the same procedure as the initial non-electrostatic adhesion test. The evaluation results of the non-electrostatic adhesion after long-term durability are shown in Table 5.

[0243] [Examples 2-30 and Comparative Examples 1-5] The low-temperature fixing and transfer properties were evaluated in the same manner as in Example 1, except that two-component developers 2 to 35 were used instead of two-component developer 1. The evaluation results are shown in Table 5.

[0244] [Table 5]

Claims

1. A toner having toner particles containing a binder resin, and organosilicon polymer particles on the surface of the toner particles, The binder resin contains a crystalline resin, When a test piece obtained by pelletizing the toner is measured using a microcompression tester at 25°C, and the Young's modulus is measured using a microcompression tester at 25°C using one particle of the organosilicon polymer particles separated from the toner, and the Young's modulus is measured using a microcompression tester at 25°C, and the Young's modulus is measured using a microcompression tester, then the relationship between TE and SiE is as follows: 800 ≤ TE ≤ 2500 1.5 ≤ SiE / TE ≤ 10.0 A toner characterized by satisfying the following conditions.

2. The toner according to claim 1, wherein the content of the crystalline resin is 50% by mass or more, based on the binder resin.

3. The toner according to claim 1 or 2, wherein the content of the organosilicon polymer particles is 0.5 parts by mass or more and 20.0 parts by mass or less per 100 parts by mass of toner particles.

4. The toner according to claim 1 or 2, wherein the toner has diffraction peaks in the range of diffraction angle 2θ of 20.0° to 22.0° in an X-ray diffraction spectrum using CuKα rays.

5. The crystalline resin has monomer units represented by the following formula (1): The toner according to claim 1 or 2, wherein the proportion of the monomer units is 30.0% by mass or more, based on the mass of the crystalline resin. 【Chemistry 1】 (In formula (1), R Z1 R represents a hydrogen atom or a methyl group. 1 (This represents an alkyl group with 18 to 36 carbon atoms.)

6. The toner particles contain an amorphous resin, When the cross-section of the toner particles was observed using a transmission electron microscope, amorphous resin domains were observed in the cross-section. The toner according to claim 1 or 2, wherein, in the cross-section, the number-average particle size of the domains located within 800 nm from the surface of the toner particles is 20 nm or more and 500 nm or less.

7. The aforementioned organosilicon polymer particles are used as the sample. 29 In Si-NMR measurements, when the total peak area originating from the organosilicon polymer is denoted as SA, the peak area originating from Q units as S4, the peak area originating from T units as S3, and the peak area originating from D units as S2, 0.20 ≤ S4 / SA ≤ 0.60 0.00 ≤ S3 / SA ≤ 0.50 0.20 ≤ S² / SA ≤ 0.70 The toner according to claim 1 or 2, satisfying the requirements.

8. The toner according to claim 1 or 2, wherein the average circularity of the toner is 0.930 or more and 0.980 or less.

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