Toner and Toner Manufacturing Method

Abstract

To provide a toner which offers improved durability while outputting images over a long period of time and suppresses ghost images and image defects, and to provide a method of manufacturing the toner.SOLUTION: A toner provided herein comprises toner particles and external additive containing composite particles comprising organosilicon polymer particles and inorganic particles present on surfaces of the organosilicon polymer particles. In a surface image of the composite particles as obtained by making surface observation using a scanning electron microscope, three or more inorganic particles are present in a surface image of one composite particle.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Conventionally, in electrophotographic image formation, external additives such as silica particles are added to the surface of toner particles to improve the fluidity, chargeability, and transferability of the electrostatic image developing toner (hereinafter simply referred to as "toner") (Patent Document 1). In recent years, with the widespread adoption of electrophotographic full-color photocopiers, there has been a growing demand for more durable and stress-resistant toners to achieve higher image quality, faster print speeds, and greater energy efficiency to reduce environmental impact. In particular, when printing images with low print density for extended periods, or when printing images in high-temperature and high-humidity environments, the toner comes into frequent contact with carriers and other components, putting it under stress. In such environments, silica particles become embedded on the surface of the toner particles, causing significant changes in the toner's surface condition. This leaves room for improvement in terms of toner's flow stability and charge stability. Therefore, as one means of improving the durability and stress resistance of toner, it has been proposed to add polymethylsilsesquioxane particles to the surface of toner particles (see, for example, Patent Documents 2 and 3). Patent Document 2 describes how to improve the fluidity, chargeability, and transferability of toner by adding silicone particles such as polymethylsilsesquioxane particles to the surface of colored particles containing a binder resin and a colorant. Similarly, Patent Document 3 describes how coating the surface of toner particles containing a binder resin and a colorant with polymethylsilsesquioxane powder imparts fluidity to the toner, preventing aggregation of toner particles and enabling the formation of images without fogging. Furthermore, Patent Documents 4 and 5 describe examples in which polyalkylsilsesquioxane particles are added to toner particles to improve the fluidity and electrostatic stability of the toner. Furthermore, Patent Document 6 proposes that by including polyorganosilsesquioxane particles in an external additive and specifying the particle size and the state of the binder resin contained in the toner particles, the polyorganosilsesquioxane particles will not detach, thereby preventing image defects and contamination of the image forming apparatus over a long period of time. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2007-99582 [Patent Document 2] Japanese Patent Application Publication No. 7-114213 [Patent Document 3] Japanese Unexamined Patent Publication No. 63-101854 [Patent Document 4] Patent No. 6116711 [Patent Document 5] Japanese Patent Publication No. 2018-4949 [Patent Document 6] Japanese Patent Publication No. 2017-122873 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] However, when using polyorganosilsesquioxane particles described in Patent Documents 2 to 6 as an external additive with the small particle size toners used in recent years, prolonged image output sometimes resulted in poor cleaning performance and image defects such as ghosting and image flaws. [Means for solving the problem]

[0005] The present invention relates to a toner having toner particles and an external additive, The external additive contains composite particles having organosilicon polymer particles and inorganic particles present on the surface of the organosilicon polymer particles. In the surface image of the composite particles obtained by surface observation using a scanning electron microscope, for one composite particle, three or more of the inorganic particles are present in the surface image. And, When a luminance histogram is created for the composite particle surface observation using a scanning electron microscope, the luminance histogram includes, (i) Peak A including the low-luminance maximum P1, (ii) Peak B including the high-luminance maximum P2, (iii) The local minimum V between P1 and P2, There exists, Peak A is a peak originating from the organosilicon polymer particles, and peak B is a peak originating from the inorganic particles. In the luminance histogram, peak A and peak B are separated by the minimum value V as the boundary, and when the area of ​​peak A is S1 and the area of ​​peak B is S2, 0.68 ≥ S² / (S1+S²) ≥ 0.10 satisfies It is a toner characterized by the above. The present invention is also a method for manufacturing a toner for manufacturing a toner having the above configuration, A composite particle forming step of mixing the organosilicon polymer particles and the inorganic particles to form the composite particles, After the composite particle forming step, an external addition step of mixing the composite particles and the toner particles to externally add the composite particles to the toner particles, It is a method for manufacturing a toner characterized by including the above.

Effects of the Invention

[0006] According to the present invention, there are provided a toner and a method for manufacturing a toner that can improve the durability of the toner in long-term image output and suppress ghosting and image defects by maintaining good cleaning properties.

Brief Description of the Drawings

[0007] [Figure 1] It is a schematic explanatory view of a surface heat treatment apparatus for toner particles. [Figure 2] It is an explanatory view of a test chart used for evaluating the occurrence of ghosting. [Figure 3] It is an explanatory view of a method for evaluating the occurrence of ghosting. [Figure 4] This is an explanatory diagram of a ghost. [Modes for carrying out the invention]

[0008] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be combined in any way.

[0009] [Features of the present invention] The inventors believe the mechanism by which the effects of the present invention are realized is as follows.

[0010] Conventional polyorganosilsesquioxane particles are nearly spherical with almost no surface irregularities. As a result, when these particles migrate to the surface of the photosensitive drum, they tend to roll around and rotate in the cleaning nip, making it difficult for them to stay in place. Consequently, they move along with the rotation of the photosensitive drum, causing image ghosting.

[0011] Furthermore, because the toner does not easily remain in the nip area, a stable blocking layer that blocks the toner is not easily formed at the edge of the cleaning blade, which makes it easier for the toner to approach the nip area. In the nip area, frictional heat is generated due to the friction between the photosensitive drum and the cleaning blade, so the toner that approaches the nip area is heated by the frictional heat and fuses to the surface of the photosensitive drum, causing image defects.

[0012] To solve this problem, we focused on the shape of the external additive and conducted thorough research. As a result, we found that it is important for the external additive to be spherical and have an uneven, textured surface.

[0013] If the surface has a highly uneven and undulating shape, the external additives tend to catch on each other and do not roll easily, so they do not rotate even if they get stuck in the cleaning nip. Therefore, we believe that the external additives tend to remain in the nip and form a stable toner block layer. In addition, we believe that the near-spherical shape makes it easier to form a block layer filled with high density external additives, making it difficult for toner to penetrate into the block layer, and thus suppressing fusion by blocking the toner at a position far from the nip.

[0014] The inventors conducted extensive research from the above perspectives. As a result, they discovered that by having inorganic particles on the surface of organosilicon polymer particles, a toner with good cleaning properties and the ability to suppress image defects can be obtained, leading to the present invention.

[0015] Specifically, the present invention relates to a toner having toner particles and an external additive, The external additive contains composite particles having organosilicon polymer particles and inorganic particles present on the surface of the organosilicon polymer particles. The toner is characterized in that, in the surface image of the composite particles obtained by surface observation using a scanning electron microscope, three or more inorganic particles are present in the surface image of each composite particle.

[0016] [Composite particles] This invention provides a detailed description of composite particles (hereinafter referred to as "composite particles") having organosilicon polymer particles and inorganic particles present on the surface of the organosilicon polymer particles.

[0017] The composite particles have three or more inorganic particles on the surface of each organosilicon polymerized particle, resulting in a round shape with a highly irregular surface, and this shape is characterized by shape factors SF-1 and SF-2.

[0018] The shape factor SF-1 is an index that indicates the degree of roundness of a particle, as shown in equation (1). A value of 100 indicates a perfect circle, and as the value increases, the particle moves further away from a circle and becomes irregular in shape.

[0019] Furthermore, the shape factor SF-2 is an index that indicates the degree of unevenness of the particle shown in equation (2). A value of 100 indicates a perfect circle, and a larger value indicates that the particle has larger protrusions. SF-1 = (maximum particle length) 2 / (Particle area) × π / 4 × 100 Equation (1) SF-2 = (perimeter of the particle) 2 / (Particle area) × 1 / (4 × π) × 100 Equation (2)

[0020] In the present invention, it is preferable that the shape coefficient SF-1 of the composite particles is 10⁸ or less and SF-2 is 400 or less. When SF-1 is 10⁸ or less and SF-2 is 400 or less, the packing density of the composite particles forming the block layer is increased, thereby improving robustness.

[0021] Furthermore, it is preferable that the shape factor SF-2 is 225 or higher. When SF-2 is 225 or higher, the composite particles in the block layer tend to catch on each other and are less likely to roll, thus improving the stability of the toner block layer.

[0022] Furthermore, by satisfying the condition 0.10 ≤ R2 / R1 ≤ 0.40, when R1 is the number-average particle size of the organosilicon polymer particles constituting the composite particles and R2 is the number-average particle size of the inorganic particles, the stability of the toner block layer can be further improved.

[0023] One method for obtaining the composite particles used in this invention is to mix organosilicon polymer particles and inorganic particles. Examples of mixers include FM mixers (manufactured by Nippon Coke Industries Co., Ltd.), Super Mixers (manufactured by Kawata Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Corporation), Hybridizers (manufactured by Nara Machinery Co., Ltd.), and Shakers (YS-8D type: manufactured by Yayoi Co., Ltd.). If the amount of raw materials to be input is small relative to the scale of the mixer, a scaled-down version of the above mixer may be manufactured and used.

[0024] Furthermore, after mixing, the coarse particles may be sieved away. Examples of sieving devices used for this purpose include the Ultrasonic (manufactured by Koei Sangyo Co., Ltd.), Resona Sieve, Gyro Shifter (manufactured by Tokuju Kogyo Co., Ltd.), Vibrasonic System (manufactured by Dalton Co., Ltd.), Soniclean (manufactured by Shinto Kogyo Co., Ltd.), Turbo Screener (manufactured by Freund Turbo Industries Ltd.), and Micro Shifter (manufactured by Makino Sangyo Co., Ltd.).

[0025] Next, it is preferable to hydrophobize the material with a hydrophobic agent such as a silane compound after sieving.

[0026] Furthermore, prior to the mixing process that forms the composite particles described above, an oil treatment step may be performed on the inorganic particles, or a fatty acid treatment step may be performed on the organosilicon polymer particles. This strengthens the bond between the organosilicon polymer particles and the inorganic particles, resulting in the formation of a more stable toner block layer.

[0027] Examples of oils used in the oil treatment process include silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.

[0028] Methods for silicone oil treatment include directly mixing silica treated with a silane coupling agent with silicone oil using a mixer such as an FM mixer, spraying silicone oil onto a base silica, or dissolving or dispersing silicone oil in a suitable solvent, then adding silica and mixing, followed by removing the solvent.

[0029] Alternatively, after the silicone oil treatment described above, the inorganic particles may be heated to a temperature of 200°C or higher in an inert gas to stabilize the surface coating.

[0030] Examples of fatty acids used in the fatty acid processing process include stearic acid, oleic acid, and lauric acid.

[0031] Methods for fatty acid treatment include, for example, heating and dissolving the fatty acids to make them liquid and then spraying them, and directly mixing finely powdered fatty acids using a mixer such as an FM mixer.

[0032] The structure of the resulting composite particles is identified by a luminance histogram of backscattered electron images obtained using a scanning electron microscope.

[0033] Backscattered electron images obtained from a scanning electron microscope are also called compositional images. Substances with smaller atomic numbers appear darker, while those with larger atomic numbers appear brighter.

[0034] Inorganic particles, such as silica, are composed only of silicon and oxygen atoms, whereas organosilicon polymer particles have an organic portion mainly composed of carbon. Therefore, in backscattered electron images of composite particles, inorganic particles have high brightness, while the exposed surface of the organosilicon polymer not covered by inorganic particles has low brightness.

[0035] Therefore, the luminance histogram of the backscattered electron image of the composite particles has two peaks: one originating from the organosilicon polymer and another originating from the inorganic particles.

[0036] Specifically, the brightness histogram for composite particles includes: (i) Peak A including the low-luminance maximum P1, (ii) Peak B including the high-luminance maximum P2, (iii) The local minimum V between P1 and P2, The presence of peak A, which originates from organosilicon polymer particles, and peak B, which originates from inorganic particles, allows us to identify the structure of the composite particles.

[0037] Furthermore, when the luminance histogram is divided using the minimum value V as the boundary, and the area on the peak A side is denoted as S1 and the area on the peak B side as S2, S2 / (S1+S2) represents the coverage rate by inorganic particles on the surface of the organosilicon polymer particles.

[0038] When S2 / (S1+S2) is 0.10 or higher, irregularities are formed on the surface of the composite particles, making it easier for the composite particles to catch on to each other, and thus further stabilizing the toner block layer.

[0039] Preferably, the above-mentioned composite particles are contained in an amount of 0.3 parts by mass or more per 100 parts by mass of toner particles, which makes it easier to obtain good cleaning performance and suppression of image defects.

[0040] <Organosilicon polymer particles> The organosilicon polymer particles constituting the composite particles are preferably condensed polymers of organosilicon compounds having a structure represented by the following formula (A).

[0041] [ka] (In formula (A), R1, R2, R3, and R4 each independently represent an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4, more preferably 1 or 2 carbon atoms), a phenyl group, or a reactive group (for example, a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)).

[0042] The method for producing organosilicon polymer particles is not particularly limited. For example, they can be obtained by dropping a silane compound into water, hydrolyzing and condensing it with a catalyst, and then filtering and drying the resulting suspension. The number-average particle size of the primary particles of the organosilicon polymer particles can be controlled by the type of catalyst, the mixing ratio, the reaction initiation temperature, and the dropping time.

[0043] Examples of catalysts include acidic catalysts and basic catalysts. Acidic catalysts facilitate hydrolysis reactions, while basic catalysts facilitate condensation reactions. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0044] Organosilicon polymer particles are obtained as follows.

[0045] We use an organosilicon compound (tetrafunctional silane) having four reactive groups in one molecule, as shown in formula (A).

[0046] In formula (A), R1 is an alkyl group or a phenyl group, and an organosilicon compound (trifunctional silane) having three reactive groups (R2, R3, R4) is used.

[0047] An organosilicon compound (difunctional silane) is used in which R1 and R2 in formula (A) are alkyl groups or phenyl groups, and which have two reactive groups (R3 and R4).

[0048] An organosilicon compound (monofunctional silane) is used in which R1, R2, and R3 in formula (A) are alkyl groups or phenyl groups, and one reactive group (R4) is present.

[0049] The above-mentioned reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure, thereby yielding an organosilicon polymer. The hydrolysis, addition polymerization, and condensation polymerization of R2, R3, and R4 can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0050] Examples of the above-mentioned tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanatesilane.

[0051] The above trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, Examples include ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane, and pentyltrimethoxysilane.

[0052] Examples of the above-mentioned bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethyldimethoxysilane, diethoxydimethylsilane, and diethyldimethoxysilane.

[0053] Examples of the above-mentioned monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, trimethylmethoxysilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0054] Furthermore, the organosilicon polymer particles are preferably polyorganosilsesquioxane.

[0055] Polyorganosylsesquioxane can be obtained by polymerizing a monomer raw material containing an organosilicon compound in which, as a trifunctional silane in the above formula (A), R1 is an alkyl group or a phenyl group, and R2, R3, and R4 are each independently hydrolyzable groups.

[0056] The trifunctional silane may be present as a single element or as a combination of two or more elements in the monomer raw material.

[0057] A hydrolyzable group refers to a functional group that is converted to a hydroxyl group after a hydrolysis reaction. Examples of hydrolyzable groups include at least one substituent selected from the group consisting of halogen functional groups (fluoro, chloro, bromo, and iodo groups), alkoxy groups, and acyloxy groups. Among these, alkoxy groups and acetoxy groups are preferred, and more preferably, at least one substituent selected from the group consisting of methoxy, ethoxy, propoxy, and acetoxy groups. These hydrolyzable groups are preferred because, upon hydrolysis, they are converted to a silyl alcohol structure, which is then easily converted to a polysiloxane skeleton or crosslinked structure through polycondensation.

[0058] As a result, the polyorganosilsesquioxane of the present invention is obtained by including the T unit structure shown in formula (2) below in the organosilicon polymer particles. R-SiO 3 / 2 ... (2) (In formula (2), R represents an alkyl group or phenyl group having 1 to 6 carbon atoms.)

[0059] The content of the T unit structure in the polyorganosilsesquioxane of the present invention is not particularly limited, but preferably it is 80 mol% or more relative to the total amount of siloxane constituent units. This makes it less susceptible to deformation under stress and less likely to become embedded on the toner particle surface. As a result, the durability of the toner in long-term image output can be improved.

[0060] The organosilicon polymer particles preferably have a number-average particle size of 30 nm or more and 150 nm or less.

[0061] <Inorganic particles> Silica particles, titania particles, strontium titanate particles, and alumina particles are particularly preferred as inorganic particles constituting the composite particles. Furthermore, composite oxide particles using two or more metals can be used, and one of these particle groups can be used alone, or two or more can be selected in any combination.

[0062] Among these, silica particles are preferred as inorganic particles. Methods for producing silica include wet silica such as the sedimentation method and the sol-gel method, and dry silica such as the deflagration method and the fumed method, with sol-gel silica being preferred among these.

[0063] Generally, sol-gel silica is silica produced by reacting tetraalkoxysilane, the raw material, with an alcohol containing an alkaline catalyst. It has a narrow particle size distribution and is less prone to aggregation. Therefore, it is easily dispersed on the surface of organosilicon polymer particles, and the resulting surface irregularities facilitate the formation of a stable toner block layer.

[0064] Furthermore, by having the number-average particle size of the inorganic particles constituting the composite particles be between 5 nm and 60 nm, the stability of the toner block layer can be further improved.

[0065] Furthermore, these inorganic particles may be used separately in combination with composite particles from the viewpoint of toner fluidity and electrostatic properties, and may be used individually or in combination of two or more types.

[0066] [Low density particles] By using particles with low density as an external additive in combination with the composite particles used in this invention, the particles become more likely to catch on to each other, further improving the stability of the toner block layer.

[0067] The density is expressed by the following formula, and a lower value indicates a shape with more concavities. Specifically, it is preferable that the density value be 0.87 or less. Condensity = (Area of ​​the particle's projection) / (Area of ​​the convex hull in the particle's projection) Equation (3)

[0068] A preferred example of low-density particles is silica fine powder, which is easier to control in terms of creating many recesses, and more specifically, dry silica.

[0069] The method for producing dry silica involves using silicon tetrachloride as a raw material, such as a silicon halogen compound, vaporizing the raw material, and then reacting it with water, which is produced as an intermediate in an oxyhydrogen flame (flame hydrolysis reaction).

[0070] Specifically, oxygen gas is supplied to the burner, the ignition burner is ignited, then hydrogen gas is supplied to the burner to form a flame, and silicon tetrachloride, the raw material, is added to it and gasified.

[0071] The average particle size and shape can be arbitrarily adjusted to create silica with many depressions by appropriately changing the silicon tetrachloride flow rate, oxygen gas supply flow rate, hydrogen gas supply flow rate, and the residence time of silica in the flame.

[0072] While silicon tetrachloride is used as the silicon halogen compound, silanes such as methyltrichlorosilane and trichlorosilane can also be used as raw materials individually, or as a mixture of silicon tetrachloride and silanes.

[0073] Low-density particles are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof.

[0074] For low-density particles, it is preferable that the number-average particle size is between 10 nm and 300 nm.

[0075] [Method for adding composite particles, etc., to toner particles] The toner of the present invention is obtained by mixing toner particles with an external additive consisting of the aforementioned composite particles and, if necessary, low-density particles or inorganic particles.

[0076] The mixing method is not particularly limited, and known mixers such as Henschel mixers, double cone mixers, V-type mixers, drum-type mixers, super mixers, Nauta mixers, Mechano Hybrid (manufactured by Nippon Coke Industries Co., Ltd.), and Novilta (manufactured by Hosokawa Micron Corporation) can be used.

[0077] Furthermore, heat treatment may be applied after the above mixing, and additional additives may be mixed after the heat treatment. Heat treatment increases the adhesion of the composite particles to the toner particles, making it easier to achieve the effect of suppressing image ghosting. Details of the heat treatment will be described later.

[0078] [Developer] The toner in this invention can be used as a one-component developer, but it can also be mixed with a magnetic carrier and used as a two-component developer in order to suppress charge localization on the toner surface.

[0079] As magnetic carriers, generally known ones can be used, such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, their alloy particles, their oxide particles; magnetic materials such as ferrite; and 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.

[0080] [Toner particles] The following describes the constituent materials of toner particles.

[0081] <Amorphous resin> The amorphous resin used as a binder resin for toner particles in the present invention is not particularly limited, and the following polymers or resins can be used.

[0082] For example, monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethacrylate methyl copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers can be used. Among these, polyester resin is preferred as the main component from the viewpoint of low-temperature fixability.

[0083] <Crystalline resin> The toner particles in this invention may contain a crystalline resin. A crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).

[0084] The crystalline resin is not particularly limited, but from the viewpoint of low-temperature fixation properties, it is preferable that it be mainly composed of crystalline polyester.

[0085] Crystalline polyesters are obtained by polycondensation reaction of monomer compositions mainly comprising an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.

[0086] <Coloring agent> The toner particles in this invention may optionally contain a colorant. Examples of colorants include the following:

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] CI Solvent Blue 70 is a dye used for cyan toner.

[0092] 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.

[0093] CI Solvent Yellow 162 is a dye used for yellow toner.

[0094] <wax> The toner particles in this invention may optionally contain wax. Examples of waxes include the following:

[0095] 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.

[0096] 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 valinalic 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, and hexamethylene Saturated fatty acid bisamides such as bis-stearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyladipamide, and N,N'dioleylsebacamide; aromatic bisamides such as m-xylenebis-stearamide and N,N'distearylisophthalamide; 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; partially esterified fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils.

[0097] <Charge control agent> The toner particles in this invention may contain a charge control agent as needed. While known charge control agents can be used in the toner particles, metal compounds of aromatic carboxylic acids that are colorless, have a fast charging speed for the toner, and can stably maintain a constant charge are particularly preferred.

[0098] 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.

[0099] [Manufacturing of toner particles] Next, we will explain the manufacturing method for toner particles.

[0100] The toner manufacturing methods in this invention include the kneading and grinding method, the dissolution and suspension method, the suspension polymerization method, and the emulsification and agglutination method. The toner may be manufactured using any one of these manufacturing methods individually or in combination.

[0101] The following section details the kneading and grinding method.

[0102] <Kneading and grinding method> In the kneading and grinding method, first, the constituent materials of the toner particles—amorphous resin, colorant, and release agents and other additives added as needed—are thoroughly mixed. At this time, in order to improve the dispersibility of the colorant in the toner particles, it is preferable to mix in a masterbatch that has been pre-mixed with the amorphous resin. Next, the mixture is melt-kneaded using a known hot kneader such as a heated roll or kneader (kneading step). After that, it is mechanically ground until the desired toner particle size is reached (grinding step), and then classified to obtain toner particles with the desired particle size distribution (classification step).

[0103] (Mixing process) The melting and kneading of the toner components can be carried out using known thermal kneaders such as heated rolls or kneaders. It is preferable that the toner components are thoroughly mixed beforehand using a mixer before proceeding with the kneading process.

[0104] Examples of mixing machines include the Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the Super Mixer (manufactured by Kawata Co., Ltd.), the Ribocone (manufactured by Okawara Seisakusho Co., Ltd.), the Nauta mixer, Turbulizer, and Cyclomix (manufactured by Hosokawa Micron Co., Ltd.), the Spiral Pin Mixer (manufactured by Taiheiyo Kiko Co., Ltd.), and the Redigge mixer (manufactured by Matsubo Co., Ltd.).

[0105] Examples of hot kneaders include the KRC kneader (manufactured by Kurimoto Iron Works), the Buss-Co kneader (manufactured by Buss), the TEM type extruder (manufactured by Toshiba Machine Co.), the TEX twin-screw kneader (manufactured by Japan Steel Works), the PCM kneader (manufactured by Ikegai Iron Works), the Trimix, planetary mixer, three-roll mill, mixing roll mill, and kneader (manufactured by Inoue Seisakusho), the Nidex (manufactured by Mitsui Mining Co.), the MS type pressure kneader and Nidarruder (manufactured by Moriyama Seisakusho), and the Banbury mixer (manufactured by Kobe Steel, Ltd.).

[0106] (Grinding process) The grinding process involves cooling the kneaded material obtained in the kneading process to a hardness suitable for grinding, and then mechanically grinding it to a toner particle size using a known grinder such as a collision plate jet mill, a fluidized bed jet mill, or a rotary mechanical mill. From the viewpoint of grinding efficiency, it is desirable to use a fluidized bed jet mill as the grinder.

[0107] Examples of crushing machines include counter jet mills, micron jets, inomizers (manufactured by Hosokawa Micron Co., Ltd.); IDS type mills, PJM jet crushers (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); cross jet mills (manufactured by Kurimoto Iron Works Co., Ltd.); Ulmax (manufactured by Nisso Engineering Co., Ltd.); SK Jet-O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Cryptron (manufactured by Kawasaki Heavy Industries Co., Ltd.); Turbo Mill (manufactured by Turbo Industries Co., Ltd.); and Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

[0108] (Classification process) The classification process involves classifying the finely ground material obtained in the grinding process described above to obtain toner with a desired particle size distribution.

[0109] Known classifiers such as wind classifiers, inertial classifiers, and sieve classifiers can be used for classification. Specifically, examples include Crusseal, Micron Classifier, Spedick Classifier (manufactured by Seishin Corporation); Turbo Classifier (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboflex (ATP), TSP Separator (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); and YM Microcut (manufactured by Yaskawa Trading Co., Ltd.).

[0110] [Heat treatment process after adding composite particles] Figure 1 illustrates a specific method for performing heat treatment on toner particles to which composite particles have been added (hereinafter referred to as "resin particles" in this explanation), using the heat treatment apparatus shown in Figure 1.

[0111] Resin particles supplied in a fixed quantity by the raw material quantitative supply means 1 are guided by compressed gas adjusted by the compressed gas flow rate adjustment means 2 into an introduction pipe 3 installed vertically along the raw material supply means. The mixture that has passed through the introduction pipe 3 is uniformly dispersed by a conical projection member 4 located in the center of the raw material supply means, and is guided into eight radially spreading supply pipes 5 and then into a processing chamber 6 where heat treatment is performed.

[0112] At this time, the flow of resin particles supplied to the processing chamber 6 is restricted by a restricting means 9 provided within the processing chamber 6 to regulate the flow of resin particles. As a result, the resin particles supplied to the processing chamber 6 are heat-treated while swirling within the processing chamber 6, and then cooled.

[0113] Hot air for heat-treating the supplied resin particles is supplied from a hot air supply means 7, distributed by a distribution member 12, and introduced into the processing chamber 6 in a spiral motion by a swirling member 13 for swirling the hot air. The swirling member 13 for swirling the hot air has multiple blades, and the swirling of the hot air can be controlled by the number and angle of the blades. The temperature of the hot air supplied into the processing chamber 6 is preferably 100°C to 300°C at the outlet of the hot air supply means 7, and more preferably 130°C to 170°C. If the temperature at the outlet of the hot air supply means 7 is within the above range, it is possible to process the particles uniformly while preventing the particles from fusing or coalescing due to overheating.

[0114] Hot air is supplied from the hot air supply means 7. Furthermore, the heat-treated resin particles are cooled by cold air supplied from the cold air supply means 8. The temperature of the cold air supplied from the cold air supply means 8 is preferably between -20°C and 30°C. If the temperature of the cold air is within the above range, the heat-treated resin particles can be cooled efficiently, preventing fusion and coalescence of the heat-treated resin particles without hindering uniform heat treatment of the resin particles. The absolute moisture content of the cold air is 0.5 g / m³. 3 More than 15.0g / m 3 The following is preferable:

[0115] Next, the cooled heat-treated resin particles are collected by a collection means 10 located at the lower end of the processing chamber 6. A blower (not shown) is provided at the end of the collection means 10, and the particles are transported by suction using this blower.

[0116] Furthermore, the powder particle supply port 14 is positioned so that the swirling direction of the supplied resin particles and the swirling direction of the hot air are the same, and the recovery means 10 is also positioned tangentially on the outer periphery of the processing chamber 6 to maintain the swirling direction of the swirled resin particles. In addition, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer periphery of the apparatus to the circumferential surface of the processing chamber. The swirling direction of the pre-heat-treated resin particles supplied from the powder particle supply port 14, the swirling direction of the cold air supplied from the cold air supply means 8, and the swirling direction of the hot air supplied from the hot air supply means 7 are all the same. As a result, turbulence does not occur in the processing chamber, the swirling flow within the apparatus is strengthened, a strong centrifugal force is applied to the pre-heat-treated resin particles, and the dispersibility of the pre-heat-treated resin particles is further improved, making it possible to obtain heat-treated resin particles with fewer coalescing particles and a uniform shape.

[0117] [Method for measuring physical properties] The following describes various measurement methods, etc.

[0118] <Measurement method for SF-1 and SF-2 composite particles> The shape factors SF-1 and SF-2 of the composite particles are measured using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.).

[0119] Observe the toner containing the composite particles and calculate the following. The observation magnification is adjusted as appropriate depending on the size of the composite particles. Using the image processing software "Image-Pro Plus 5.1J" (MediaCybernetics), calculate the perimeter and area of ​​100 randomly selected composite particles in a field of view magnified up to 200,000 times. SF-1 and SF-2 are calculated using the following formulas, and their average values ​​are taken as SF-1 and SF-2. SF-1 = (maximum particle length) 2 / (Particle area) × π / 4 × 100 Equation (1) SF-2 = (perimeter of the particle) 2 / (Particle area) × 1 / (4 × π) × 100 Equation (2)

[0120] Furthermore, composite particles can also be measured individually.

[0121] If the toner contains both composite particles and silica particles, the composite particles are identified by comparing the ratio of the elemental content (atomic%) of Si and O (Si / O ratio) with that of a standard sample. EDS analysis is performed on both the composite particle and silica particle standards under the same conditions to obtain the elemental content (atomic%) of Si and O. Let the Si / O ratio of the composite particles be A, and the Si / O ratio of the silica particles be B. The measurement conditions are selected such that A is significantly larger than B. Specifically, 10 measurements are performed on the standard under the same conditions, and the arithmetic mean values ​​of A and B are obtained. The measurement conditions are selected such that the average value obtained is A / B > 1.1.

[0122] <Method for measuring the density and number-average particle size of external additive particles> The density of external additive particles can be measured by adding the external additive particles to toner particles, observing the toner surface with a scanning electron microscope, and analyzing the resulting image. Specifically, for toner particles 1 (100 parts by mass) as described in the example, external additive particles (0.3 parts by mass) are mixed in an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) for 60 seconds. -1 The mixture is mixed for 5 minutes under these conditions. The toner surface is then observed using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation).

[0123] For observation, the magnification is adjusted as appropriate, up to a maximum of 200,000 times, depending on the size of the external additive particles. In addition, to process the images of the external additive particles, the acceleration voltage during observation is set to a high value (e.g., 10kV), and the images are observed as backscattered electron images.

[0124] Image processing was performed using the image analysis software Image J (developed by Wayne Rasband). By binarizing the high-luminance external additive particles and the low-luminance toner particles, the area of ​​each external additive particle and the area of ​​the convex hull within the external additive particles were calculated, and the average density was measured using the following formula (3). The binarization conditions can be appropriately selected depending on the observation equipment and sputtering conditions. Furthermore, the density of each external additive particle can be obtained using the Solidity function in the image analysis software Image J. Density = (Area of the projected image of the particles) / (Area of the convex hull in the projected image of the particles) Equation (3)

[0125] The specific measurement method is as follows.

[0126] Select 100 toner particles that exhibit a major axis R (μm) satisfying the relationship 0.9 ≦ R / D4 ≦ 1.1 with respect to the weight-based equivalent circle mean diameter D4 (μm) of the toner measured by the particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) described below. Select a relatively flat portion of the toner surface (a field of view in focus across the entire observation surface), observe one field of view per toner particle, and obtain 100 images.

[0127] (Image analysis) Calculate the average density from the obtained SEM observation images using the image processing software ImageJ (developed by Wayne Rashand). The calculation procedure is shown below. 1) Set the scale in [Analyze] - [Set Scale]. 2) Set the threshold in [Image] - [Adjust] - [Threshold]. (Set to a value that leaves no noise and leaves the externally added particles that are the measurement target) 3) Select the image portion of the externally added agent measured in [Image] - [Crop]. 4) Erase those where the externally added agents overlap by image editing. 5) Invert the black-and-white image in [Edit] - [Invert]. 6) Check [Area], [Shape Descriptors], [Perimeter], [Fit Ellipse], [Ferets Diameter] in [Analyze] - [Set Measurements]. Also, set [Redirect to] to [None] and [Decimal Place(0 - 9)] to 3. 7) In [Analyze] - [Analyze Particle], set the area of the particles to 0.005 μm 2Specify the above and execute. 8) Obtain the Solidity and Area values ​​for each particle specified in 7) above. 9) Measurements are taken for 100 observed images, and the arithmetic mean of the obtained solidity is calculated and used as the density. Similarly, the arithmetic mean of the diameter of the circle corresponding to the area indicated by the obtained Area is calculated and used as the number-average particle size.

[0128] <Scattered electron images of composite particle surfaces, and measurement of physical properties based on these images> (Method for obtaining backscattered electron images of the surface of composite particles) The backscattered electron images of the composite particle surface were acquired using a scanning electron microscope (SEM).

[0129] The following procedure is used to determine contrast and brightness. First, the contrast is set so that the two maximal values ​​P1 and P2 on the luminance histogram each have the largest possible number of pixels, and the luminance values ​​that give maximal value P1 and maximal value P2 are as far apart as possible. Note that the luminance value that gives maximal value P1 < the luminance value that gives maximal value P2.

[0130] Next, adjust the brightness so that the tails of the two peaks with maximum values ​​P1 and P2 fall within the luminance histogram. These contrast and brightness settings should be adjusted as appropriate according to the state of the equipment being used.

[0131] (Method for confirming that the peak containing the maximum value P1 originates from the organosilicon polymer) The origin of the peak containing the maximum value P1 from the organosilicon polymer can be confirmed by superimposing the elemental mapping image obtained by energy-dispersive X-ray spectroscopy (EDS) using a scanning electron microscope (SEM) with the aforementioned backscattered electron image.

[0132] The elemental mapping image derived from the organosilicon polymer obtained is superimposed with the backscattered electron image, and it is confirmed that the elemental parts derived from the organosilicon polymer in the mapping image correspond to the dark areas in the backscattered electron image.

[0133] When composite particles consist of organosilicon polymer particles and silica particles, select measurement conditions that significantly increase the ratio of Si and O elemental content (atomic%) obtained from EDS analysis for each standard of organosilicon polymer particles and silica particles. Specifically, let Z be the Si / O ratio of organosilicon polymer particles and B be the Si / O ratio of silica particles. Perform 10 measurements on the standard under the same conditions and obtain the arithmetic mean values ​​of Z and B. Select measurement conditions such that the obtained average value is Z / B > 1.1.

[0134] The Si / O ratio mapping image derived from organosilicon polymer particles, obtained under the obtained measurement conditions, is superimposed with the backscattered electron image, and it is confirmed that the Si / O ratio portion derived from the organosilicon polymer in the mapping image matches the dark area in the backscattered electron image.

[0135] (How to obtain a brightness histogram) The luminance histogram is obtained by analyzing the backscattered electron image of the outermost surface of the composite particles obtained by the above method using the image processing software ImageJ (developed by Wayne Rashand). The procedure is as follows.

[0136] First, convert the backscattered electron image to 8-bit using the Image menu's Type option. Next, reduce image noise by setting the Median diameter to 2.0 pixels using the Process menu's Filters option.

[0137] After tracing the outline of a single composite particle using the Freehand tool on the toolbar, extract only the single composite particle portion using Clear Outside, and then select Histogram from the Analyze menu to display the luminance histogram in a new window. Obtain the numerical values ​​of the luminance histogram from the List in the aforementioned window. If necessary, you may perform luminance histogram fitting.

[0138] From this, we obtain the luminance that gives the maximum value P1, the luminance that gives the maximum value P2, and the luminance that gives the minimum value V.

[0139] Then, Vk is the brightness that gives a minimum value V. S1 is the total number of pixels in the brightness range from 0 to Vk. Let S2 be the total number of pixels in the brightness range (Vk+1) to 255.

[0140] Here, for example, "luminance that gives a maximum value P1" or "luminance that gives a maximum value P2" refers to the luminance when the number of pixels reaches a maximum value P1 or a maximum value P2, respectively.

[0141] The above procedure is performed for 100 composite particles, and the average values ​​for each are taken as S1 and S2 of the composite particle obtained from the luminance histogram. The coverage of inorganic particles in the composite particle, S2 / (S1+S2), is then calculated.

[0142] (Method for analyzing the number of inorganic particles per composite particle) The number of inorganic particles is analyzed using the backscattered electron image of the outermost surface of the composite particles obtained by the above method, with the image processing software ImageJ (developed by Wayne Rashand). The procedure is as follows.

[0143] First, convert the backscattered electron image to 8-bit using the Image menu's Type option. Next, reduce image noise by setting the Median diameter to 2.0 pixels using the Process menu's Filters option.

[0144] After tracing the outline of a single composite particle using the Freehand tool on the toolbar, use Clear Outside to extract only that single composite particle.

[0145] Next, select Threshold from the Adjust menu in the Image menu. Manually select all pixels corresponding to luminance Vk and click Apply to obtain a binarized image. This operation will display pixels corresponding to S1 in black (pixel group S1) and pixels corresponding to S2 in white (pixel group S2).

[0146] Next, select Analyze Particles from the Analyze menu, check Display Result, and click OK.

[0147] The newly opened Results window displays a list of analyses for each domain covered by inorganic particles formed by the pixel group S2.

[0148] The number of rows in this analysis list represents the number of inorganic particles per composite particle.

[0149] Additionally, the area of ​​domains not in contact with the contour of the composite particle is obtained.

[0150] The above procedure is performed for 100 composite particles, and the average value for each is used to determine the number-average particle size of the inorganic particles, which is the arithmetic mean of the number of inorganic particles per composite particle and the diameter of the circle corresponding to the area represented by the inorganic particle's Area.

[0151] <Method for measuring the volume-average particle size of toner particles> The volume-average particle size 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.

[0152] 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.

[0153] Before performing measurements and analysis, configure the dedicated software as follows.

[0154] In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, 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.

[0155] 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.

[0156] The specific measurement method is as follows: (1) Pour approximately 200 ml of the 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 tube. (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 their phases shifted by 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. Approximately 2 ml of the aforementioned 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 aqueous 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 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 to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to approximately 5%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device, and the volume-average particle size is calculated.

[0157] <Confirmation of the structure of crystalline resin from toner> The molecular structure of crystalline resins, such as crystalline polyester resins, can be confirmed by known analytical methods including NMR measurements in solution or solid state, as well as X-ray diffraction, GC / MS, LC / MS, and IR measurements. Furthermore, known methods can be used to isolate crystalline resins, such as crystalline polyester resins, from toner.

[0158] Specifically, the isolation process is carried out as follows: First, the toner is dispersed in ethanol, which is a poor solvent for toner, and the temperature is raised to a level above the melting point of the crystalline resin. At this time, pressure may be applied if necessary. At this point, the crystalline resin that has exceeded its melting point has melted. Subsequently, the crystalline resin can be collected from the toner by solid-liquid separation.

[0159] <Measurement of crystalline resin content in toner> The crystalline resin content is calculated from the integral value of the nuclear magnetic resonance spectroscopy (1H-NMR) spectrum of the toner, based on the nuclear magnetic resonance spectroscopy (1H-NMR) spectra of the binder resin and the crystalline resin, respectively. 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

[0160] <Method for measuring the softening point 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.

[0161] In this invention, the softening point is defined as the "melting temperature in the 1 / 2 method" as described in the manual accompanying the "Flow Characteristics Evaluation Device Flow Tester CFT-500D". The melting temperature in the 1 / 2 method is calculated as follows: First, half of the difference between the piston descent amount Smax at the end of the outflow and the piston descent amount Smin at the start of the outflow is determined (let this be X. X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston descent amount is X is the melting temperature in the 1 / 2 method.

[0162] 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 in a tablet molding compressor (e.g., NT-100H, manufactured by NPA System Co., Ltd.) at approximately 10 MPa for approximately 60 seconds in an environment of 25°C.

[0163] The measurement conditions for the CFT-500D are as follows: Test mode: Temperature increase method Starting temperature: 40℃ 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

[0164] <Identification of the composition and ratio of constituent compounds of organosilicon polymer particles> The composition and ratio of constituent compounds of organosilicon polymer particles contained in toner are identified using pyrolysis gas chromatography-mass spectrometry (hereinafter also referred to as "pyrolysis GC / MS") and NMR. If organosilicon polymer particles are available individually, they can also be measured separately.

[0165] Pyrolysis GC / MS is used to analyze the types of constituent compounds in organosilicon polymer particles.

[0166] The types of constituent compounds of organosilicon polymer particles are identified by analyzing the mass spectra of the decomposition products derived from organosilicon polymer particles, which are generated when toner is thermally decomposed at 550°C to 700°C. The specific measurement conditions are as follows.

[0167] (Measurement conditions for pyrolysis GC / MS) ·Pyrolysis device: JPS-700 (Japan Analysis Industry) Decomposition temperature: 590℃ GC / MS instrument: Focus GC / ISQ (Thermo Fisher) Column: HP-5MS, length 60m, inner diameter 0.25mm, film thickness 0.25μm Inlet temperature: 200℃ Flow pressure: 100kPa Split: 50 mL / min MS ionization: EI Ion source temperature: 200℃ Mass range: 45-650 Next, the relative abundance of the constituent compounds of the identified organosilicon polymer particles was determined in the solid state. 29 Measured and calculated using Si-NMR.

[0168] 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 nanoparticles.

[0169] The structure bonded to Si can be identified by specifying 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

[0170] After the measurement, the silane components of the sample or organosilicon polymer fine 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. M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1) D unit structure: (Rd)(Re)Si(O 1 / 2 )2(S2) T unit structure: RfSi(O 1 / 2 )3(S3) Q Unit structure: Si(O) 1 / 2 )4(S4) Let (S1+S2+S3+S4)=SA.

[0171] In formulas (S1), (S2), and (S3), Ra, Rb, Rc, Rd, Re, and Rf represent organic groups such as hydrocarbon groups having 1 to 6 carbon atoms, halogen atoms, hydroxyl groups, acetoxy groups, or alkoxy groups bonded to silicon.

[0172] If you need to examine the structure in more detail, please refer to the 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.

[0173] From SA, S1, S2, S3, and S4 obtained in this way S1 / SA as the ratio of M-unit structures, The ratio of D unit structure is S2 / SA. S3 / SA as the ratio of the T unit structure, S4 / SA as the ratio of Q unit structure This is calculated.

[0174] If the toner contains silicon-containing materials other than organosilicon polymer particles, the toner is dispersed in a solvent such as chloroform, and then the silicon-containing materials other than organosilicon polymer particles are removed by centrifugation or other means based on the difference in specific gravity. One example of this method is shown below.

[0175] First, 1 g of toner is added to 31 g of chloroform in a vial and dispersed to separate silicon-containing materials other than organosilicon polymer particles from the toner. A dispersion solution is prepared by treating the mixture with an ultrasonic homogenizer for 30 minutes. The treatment conditions are as follows: • Ultrasonic processing equipment: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.) Microchip: Stepped microchip, tip diameter φ2mm Microchip tip position: Center of the glass vial, 5mm above the bottom of the vial. Ultrasonic conditions: Intensity 30%, 30 minutes (Apply ultrasound while cooling the vial with ice water to prevent the dispersion from overheating).

[0176] The dispersion was transferred to a 50 mL glass tube for the swing rotor and centrifuged in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) at 58.33S. -1 Centrifugation is performed for 30 minutes. After centrifugation, silicon-containing materials other than organosilicon polymer particles and the residue from which silicon-containing materials other than organosilicon polymer particles have been removed are separated in the glass tube. The residue from which silicon-containing materials other than organosilicon polymer particles have been removed from the toner is extracted and dried under vacuum conditions (40°C / 24 hours) to obtain a sample from which silicon-containing materials other than organosilicon polymer particles have been removed from the toner. The composition and ratio of constituent compounds of organosilicon polymer particles contained in the toner can be identified by the same procedure as above. [Examples]

[0177] The present invention will be described more specifically below with reference to examples, but the present invention is not limited to these examples. In the following formulations, parts are by mass unless otherwise specified.

[0178] <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 44°C. 54.4 parts of trimethoxymethylsilane were added and stirred for 2.0 hours to obtain the raw material solution.

[0179] 2. Polycondensation process In a 1000 ml beaker, 68.8 parts RO water, 340.0 parts methanol, and 2.1 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 step 1 (hydrolysis) 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 the polycondensation reaction solution.

[0180] 3.Particleization process 1000 parts of RO water were added to a 2000 ml beaker, and the polycondensation reaction solution obtained in step 2 (condensation polymerization) 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.

[0181] 4. Hydrophobization process To the dispersion containing the silicon polymer particles 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 number-average particle size of the obtained organosilicon polymer particles 1 was 130 nm.

[0182] Furthermore, the ratio of T unit structures in the obtained organosilicon polymer particles 1 was 100 mol%, and it was polyorganosilsesquioxane.

[0183] <Example of production of organosilicon polymer particles 2> Organosilicon polymer particles 2 were obtained in the same manner as in the production example of organosilicon polymer particles 1, except that trimethoxymethylsilane was not added during the hydrolysis process, but instead 22.2 parts of tetraethoxysilane, 21.5 parts of dimethyldimethoxysilane, and 10.8 parts of trimethylsilanol were added, and the stirring temperature was changed to 30°C and the stirring time to 0.5 hours. The number-average particle size of the obtained organosilicon polymer particles 2 was 130 nm.

[0184] Furthermore, the proportion of T unit structures in the obtained organosilicon polymer particles 2 was 0 mol%, the proportion of M unit structures was 20 mol%, the proportion of D unit structures was 50 mol%, and the proportion of Q unit structures was 30 mol%.

[0185] <Example of production of organosilicon polymer particles 3> Except for changing the stirring temperature to 50°C in the hydrolysis step and using 78.8 parts RO water, 330.0 parts methanol, and 1.5 parts 25% aqueous ammonia in the condensation polymerization step, organosilicon polymer particles 3 were obtained in the same manner as in the production example of organosilicon polymer particles 1. The number-average particle size of the obtained organosilicon polymer particles 3 was 30 nm.

[0186] Furthermore, the ratio of T unit structures in the obtained organosilicon polymer particles 3 was 100 mol%, and it was polyorganosilsesquioxane.

[0187] <Example of production of organosilicon polymer particles 4> Except for changing the stirring temperature to 49°C in the hydrolysis step and using 1.6 parts of 25% aqueous ammonia in the condensation polymerization step, organosilicon polymer particles 4 were obtained in the same manner as in the production example of organosilicon polymer particles 1. The number-average particle size of the obtained organosilicon polymer particles 4 was 70 nm.

[0188] Furthermore, the ratio of T unit structures in the obtained organosilicon polymer particles 4 was 100 mol%, and it was polyorganosilsesquioxane.

[0189] <Example of manufacturing of organosilicon polymer particles 5> Except for changing the stirring temperature to 47°C in the hydrolysis step and using 1.8 parts of 25% aqueous ammonia in the condensation polymerization step, organosilicon polymer particles 5 were obtained in the same manner as in the production example of organosilicon polymer particles 1. The number-average particle size of the obtained organosilicon polymer particles 5 was 100 nm.

[0190] Furthermore, the ratio of T unit structures in the obtained organosilicon polymer particles 5 was 100 mol%, and it was polyorganosilsesquioxane.

[0191] <Examples of manufacturing inorganic particles 1-6> Inorganic particles 1-4 were silica particles obtained by a general sol-gel method, inorganic particle 5 was silica particles obtained by a general fumed method, and inorganic particle 6 was strontium titanate particles obtained by an atmospheric pressure heating reaction method. The physical properties of inorganic particles 1-6 are shown in Table 1.

[0192] [Table 1]

[0193] <Example of manufacturing composite particle 1> In the composite particle formation process, Organosilicon polymer particles 1,100 parts Inorganic particles 1 0.11 parts The mixture was introduced into a modified mixer, a scaled-down version of an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), mixed, and then sieved. To 100 parts of the resulting sieved particles, 10 parts of hexamethyldisilazane were added as a surface treatment agent to obtain composite particles 1.

[0194] Analysis using the backscattered electron images described above revealed that composite particle 1 contains an average of 3 inorganic particles per particle, with a shape coefficient SF-1 of 106, SF-2 of 150, and S2 / (S1+S2) of 0.16.

[0195] <Manufacturing examples of composite particles 2-12 and 17> In the composite particle formation process, composite particles 2-12 and 17 were obtained in the same manner as in the production example of composite particle 1, except that the types of organosilicon polymer particles and inorganic particles and the amounts added to the mixer were changed, as shown in Table 2. R2 / R1, the number of inorganic particles present per composite particle, SF-1, SF-2, and S2 / (S1+S2) are shown in Table 2.

[0196] <Example of manufacturing composite particle 13> As a fatty acid treatment step, 10 parts of stearic acid were added to 100 parts of organosilicon polymer particles as a surface treatment agent to obtain surface-treated organosilicon polymer particles.

[0197] On the other hand, as an oil treatment process, surface-treated inorganic particles were obtained by adding 10 parts of silicone oil as a surface treatment agent to 100 parts of inorganic particles 1.

[0198] Subsequently, as a composite particle formation step, 1:100 parts of surface-treated organosilicon polymer particles and 1:0.32 parts of surface-treated inorganic particles were added to a mixer, mixed, and sieved to obtain composite particles 13. Table 2 shows R2 / R1, the number of inorganic particles present per composite particle, SF-1, SF-2, and S2 / (S1+S2).

[0199] <Example of manufacturing composite particle 14> As an oil treatment process, surface-treated inorganic particles were obtained by adding 10 parts of silicone oil as a surface treatment agent to 100 parts of inorganic particles 1.

[0200] Subsequently, as a composite particle formation step, 1:100 parts of surface-treated organosilicon polymer particles and 1:0.32 parts of surface-treated inorganic particles were added to a mixer, mixed, and sieved. To 100 parts of the resulting sieved particles, 5 parts of hexamethyldisilazane were added as a surface treatment agent to obtain composite particles 14. Table 2 shows the R2 / R1 ratio, the number of inorganic particles per composite particle, SF-1, SF-2, and S2 / (S1+S2).

[0201] <Examples of manufacturing composite particles 15 and 16> In the composite particle formation process, composite particles 15 and 16 were obtained in the same manner as in the production example of composite particle 13, except that the types of organosilicon polymer particles and inorganic particles and the amounts added to the mixer were changed, as shown in Table 2. R2 / R1, the number of inorganic particles present per composite particle, SF-1, SF-2, and S2 / (S1+S2) are shown in Table 2.

[0202] [Table 2]

[0203] <Low density particles> The low-density particles used as an external additive in combination with the composite particles are shown in Table 3.

[0204] [Table 3]

[0205] <Example of Amorphous Polyester Resin 1 Production> • Polyoxypropylene(2,2)-2,2-bis(4-hydroxyphenyl)propane: 73.3 parts (0.20 moles; 100.0 mol% of the total moles of polyhydric alcohols) Terephthalic acid: 22.4 parts (0.13 moles; 82.0 mol% of the total moles of polycarboxylic acids) • Adipic acid: 4.3 parts (0.03 moles; 18.0 mol% of the total moles of polycarboxylic acids) Titanium tetrabutoxide (esterification catalyst): 0.51 parts The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was stirred at 202°C and reacted for 4.5 hours to obtain amorphous polyester resin 1 as the binder resin. The softening point of the obtained amorphous polyester resin 1 was 90°C.

[0206] <Example of manufacturing crystalline polyester resin 1> Dodecanediol: 34.5 parts (0.29 moles; 100.0 mol% of the total number of moles of polyhydric alcohols) Sebacic acid: 65.5 parts (0.28 moles; 100.0 mol% of the total moles of polycarboxylic acids) The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The reaction was carried out at 140°C with stirring for 3 hours. • Tin 2-ethylhexanoate: 0.5 parts Subsequently, the above materials were added, the pressure in the reaction vessel was reduced to 8.2 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C. After that, the pressure in the reaction vessel was gradually released to return to atmospheric pressure, and crystalline polyester resin 1 was obtained. The softening point of the obtained crystalline polyester resin 1 was 81°C.

[0207] <Example of Toner 1 manufacturing> 1. Mixing process · 100 parts of amorphous polyester resin · 5.0 parts of Fischer-Tropsch wax (peak temperature (melting point) of the maximum endothermic peak: 90 °C) · 5.5 parts of C.I. Pigment Blue 15:3 The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for 5 minutes. Subsequently, they were melt-kneaded using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 135 °C to obtain a kneaded product.

[0208] 2. Crushing process The obtained kneaded product was cooled and roughly crushed to 1 mm or less using a hammer mill to obtain a roughly crushed product. The obtained roughly crushed product was finely crushed using a mechanical crusher (T-250, manufactured by Turbo Industry Co., Ltd.) to obtain a finely crushed product.

[0209] 3. Classification process Using a Facluty (F-300, manufactured by Hosokawa Micron Corporation), the obtained finely crushed product was classified to obtain toner particles 1 as classified particles with a volume average particle diameter of 5.7 μm. The operating conditions of the above Facluty were a classification rotor rotation speed of 11000 rpm and a dispersion rotor rotation speed of 7200 rpm.

[0210] 4. External addition process · 100.00 parts of toner particles 1 · 1.20 parts of composite particles 1 · 1.00 part of inorganic particles 5 · 0.70 part of inorganic particles 6 The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes, and then sieved to obtain toner 1.

[0211] <Manufacturing examples of toner 2 to 19, 22 to 24> In the external addition process, toner 2 to 19, 22 to 24 were obtained in the same manner as the manufacturing example of toner 1, except that the type and amount of the composite particles, and the type and amount of the inorganic particles and low-density particles were changed as shown in Table 4.

[0212] <Example of Toner 20 production> After obtaining toner particles 1 in the same manner as the manufacturing example of toner 1, • Toner particles 1 100.00 parts ·Composite particles 16 1.50 parts The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 1900 rpm for 3 minutes. After that, the mixture was heat-treated using the heat treatment apparatus shown in Figure 1, and then sieved to obtain heat-treated particles 1.

[0213] The operating conditions for the heat treatment device are: feed rate of 5 kg / hr, hot air temperature of 150°C, and hot air flow rate of 6 m³. 3 / min., cold air temperature -5℃, cold air flow rate 4m 3 / min., blower airflow 20m 3 / min., injection air flow rate 1m 3 I set it to / min.

[0214] Next, in the external additive process, • Heat-treated particles 1 100.00 parts ·Inorganic particles 5 1.00 parts ·Inorganic particles 6 0.70 parts The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes, and then sieved to obtain toner 20.

[0215] Other conditions were the same as in the manufacturing example for toner 1.

[0216] <Example of Toner 21 manufacturing> Except for adding 5 parts of crystalline polyester 1 during the kneading process, the kneading, grinding, and classification processes were carried out under the same conditions as in the example of toner 1 production to form toner particles 2.

[0217] Next, in the external additive process, • Toner particles 2 100.00 parts ·Composite particles 1 1.20 parts ·Inorganic particles 5 1.00 parts ·Inorganic particles 6 0.70 parts It was mixed with a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotational speed of 1900 rpm for 10 minutes, and then sieved to obtain Toner 21.

[0218] <Production Example of Toner 25> After forming Toner Particles 2 in the same manner as in the production example of Toner 21, in the external addition step, · 100.00 parts of Toner Particles 2 · 1.20 parts of Composite Particles 17 · 1.00 part of Inorganic Particles 5 · 0.70 part of Inorganic Particles 6 The above materials were mixed with a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotational speed of 1900 rpm for 10 minutes, and then sieved to obtain Toner 25.

[0219]

Table 4

[0220] <Production Example of Magnetic Core Particles 1> · Step1 (weighing and mixing step): 62.7 parts of Fe2O3 29.5 parts of MnCO3 6.8 parts of Mg(OH)2 1.0 part of SrCO3 The ferrite raw materials were weighed so as to have the above composition ratio. Then, it was pulverized and mixed for 5 hours with a dry vibration mill using stainless steel beads with a diameter of 1 / 8 inch.

[0221] · Step2 (precalcination step): The obtained pulverized product was made into pellets of about 1 mm square with a roller compactor. Coarse powder was removed from these pellets with a vibrating sieve having a mesh size of 3 mm, and then fine powder was removed with a vibrating sieve having a mesh size of 0.5 mm. After that, using a burner-type firing furnace, it was fired at a temperature of 1000 °C for 4 hours in a nitrogen atmosphere (oxygen concentration: 0.01% by volume) to produce precalcined ferrite. The composition of the obtained precalcined ferrite is as follows. (MnO)a(MgO)b(SrO)c(Fe2O3)d In the above formula, a=0.257, b=0.117, c=0.007, d=0.393

[0222] • Process 3 (Grinding process): After crushing the calcined ferrite to approximately 0.3 mm using a crusher, 30 parts water was added to 100 parts calcined ferrite using 1 / 8-inch diameter zirconia beads, and the mixture was ground in a wet ball mill for 1 hour. The resulting slurry was then ground in a wet ball mill using 1 / 16-inch diameter alumina beads for 4 hours to obtain a ferrite slurry (finely ground calcined ferrite).

[0223] ·Process 4 (granulation process): To a ferrite slurry, 1.0 part of ammonium polycarboxylate was added as a dispersant and 2.0 parts of polyvinyl alcohol as a binder per 100 parts of calcined ferrite. The mixture was then granulated into spherical particles using a spray dryer (manufactured by Okawara Chemical Machinery). After adjusting the particle size of the resulting particles, they were heated in a rotary kiln at 650°C for 2 hours to remove the organic components of the dispersant and binder.

[0224] • Process 5 (Baking Process): To control the firing atmosphere, the product was heated in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00 vol%) from room temperature to 1300°C in 2 hours, and then fired at 1150°C for 4 hours. After that, the temperature was cooled to 60°C over 4 hours, the atmosphere was changed from nitrogen to air, and the product was removed at a temperature of 40°C or lower.

[0225] • Process 6 (sorting process): After crushing the aggregated particles, low-magnetic-force particles were cut by magnetic separation, and coarse particles were removed by sieving with a 250 μm mesh sieve to obtain magnetic core particles 1 with a 50% particle size (D50) of 37.0 μm based on volume distribution.

[0226] <Preparation of coating resin 1> Cyclohexyl methacrylate monomer 26.8% by mass Methyl methacrylate monomer 0.2% by mass Methyl methacrylate macromonomer 8.4% by mass (A macromonomer with a weight-average molecular weight of 5000, having a methacryloyl group at one end.) Toluene 31.3% by mass Methyl ethyl ketone 31.3% by mass Azobisisobutyronitrile 2.0% by mass Of the above materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirrer. Nitrogen gas was introduced to create a sufficient nitrogen atmosphere, and the mixture was heated to 80°C. Then, azobisisobutyronitrile was added and polymerization was carried out under reflux for 5 hours. Hexane was injected into the resulting reaction product to precipitate the copolymer, and after filtering the precipitate, it was vacuum dried to obtain coating resin 1.

[0227] The obtained 30 parts of coating resin 1 were dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain polymer solution 1 (solid content 30% by mass).

[0228] <Preparation of coating resin solution 1> Polymer solution 1 (resin solids concentration 30%) 33.3% by mass Toluene 66.4% by mass Carbon black (Regal330; manufactured by Cabot) 0.3% by mass (Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m 2 / g, DBP oil absorption 75ml / 100g) The mixture was dispersed for 1 hour using zirconia beads with a diameter of 0.5 mm in a paint shaker. The resulting dispersion was filtered through a 5.0 μm membrane filter to obtain coating resin solution 1.

[0229] <Manufacturing example of magnetic carrier 1> (Resin coating process): In a vacuum-degassed kneader maintained at room temperature, coating resin solution 1 was added in an amount of 2.5 parts resin component per 100 parts magnetic core particles 1. After adding the solution, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes. Once a certain amount (80% by mass) of the solvent had evaporated, the temperature was raised to 80°C while mixing under reduced pressure, and the toluene was removed by distillation over 2 hours, after which the mixture was cooled.

[0230] The obtained magnetic carriers were separated for low magnetic force by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified using an air classifier to obtain magnetic carrier 1 with a 50% particle size (D50) of 38.2 μm based on volume distribution.

[0231] <Manufacturing examples of two-component developers 1-25> To a magnetic carrier 1, toners 1 to 25 were added so that the toner concentration was 7.5% by mass, and the mixture was mixed using a V-type mixer (V-10 model: Tokuju Seisakusho Co., Ltd.) for 0.5 seconds. -1 The two-component developers 1-25 were obtained by mixing under conditions of a rotation time of 5 min, and are shown in Table 5. The physical properties measured for the toner are also shown in Table 5.

[0232] [Table 5]

[0233] [Example 1] The performance evaluation of the two-component developer 1 was conducted according to the following procedure.

[0234] <Transcriptional evaluation> A modified Canon imageRUNNER ADVANCE C5560 digital commercial printer was used as the image forming apparatus.

[0235] The image forming apparatus has a photoreceptor that forms an electrostatic latent image as an image carrier, and a developing step in which the electrostatic latent image of the photoreceptor is developed as a toner image using a two-component developer. Furthermore, it has a transfer step in which the developed toner image is transferred to an intermediate transfer body, and then the toner image of the intermediate transfer body is transferred to paper, and a fixing step in which the toner image on the paper is fixed by heat.

[0236] The modifications to the device 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 FFh image (solid color image) with the desired aspect ratio was output, and VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image was as desired, and the evaluation described below was performed. FFh is a value representing 256 gradations in hexadecimal, where 00h is the first gradation of 256 gradations (white area), and FFh is the 256th gradation of 256 gradations (solid color area).

[0237] Transfer efficiency is an indicator of transferability, showing what percentage of the toner developed on the photosensitive drum is transferred to the intermediate transfer belt.

[0238] Developer 1 was added to the developer in the cyan station of this image forming apparatus, and the transfer efficiency was measured using the following procedure.

[0239] First, 100 solid images were printed. Then, the image formation process was carried out up to the point where toner was transferred to the intermediate transfer belt. The toner transferred to the intermediate transfer belt and the toner remaining on the photosensitive drum after transfer were peeled off using transparent polyester adhesive tape. The density difference was calculated by subtracting the toner density of the paper with only the adhesive tape applied from the density of the paper with only the adhesive tape applied. Transfer efficiency is the ratio of the toner density difference on the intermediate transfer belt to the sum of the respective toner density differences, which is set to 100. A higher ratio indicates better transfer efficiency.

[0240] The measurements were taken under normal temperature and low humidity (NL) conditions (temperature 23°C, relative humidity 5%), and the transfer efficiency was judged according to the following evaluation criteria.

[0241] The toner density was measured using a "504 spectrophotometer" (manufactured by X-Rite).

[0242] (Evaluation Criteria) A: Transfer efficiency of 98% or higher B: Transfer efficiency is between 95% and 98% C: Transcription efficiency is between 92% and 95%. D: Transcription efficiency is between 89% and 92%. E: Transcription efficiency is less than 89% In the above evaluation criteria, A to C were defined as acceptable levels in the present invention, D as the level of the prior art, and E as an unacceptable level in the present invention. The results are shown in Table 6.

[0243] <Evaluation of post-transferability after durability> Paper: CS-680 (68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner coverage on paper: 0.35 mg / cm² 2 (FFh image) (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: A grid chart with a 30% image ratio covering the entire surface of the A4 paper shown above. Test environment: Normal temperature and low humidity (NL) environment (temperature 23°C, relative humidity 5%R) H) Process speed: 450 mm / sec After printing 100,000 of the above evaluation images, the above transferability evaluation was performed.

[0244] (Evaluation Criteria) A: Transfer efficiency of 95% or higher B: Transcription efficiency is between 92% and 95% C: Transcription efficiency is between 89% and 92%. D: Transcription efficiency is between 86% and 89%. E: Transcription efficiency is less than 86% In the above evaluation criteria, A to C were defined as acceptable levels in the present invention, D as the level of the prior art, and E as an unacceptable level in the present invention. The results are shown in Table 6.

[0245] <Evaluation of Cleanability> Paper: CS-680 (68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner coverage on paper: 0.35 mg / cm² 2 (FFh image) (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: A grid chart with a 30% image ratio covering the entire surface of the A4 paper shown above. Test environment: High temperature and high humidity environment (temperature 30°C / humidity 80%RH (hereinafter H / H)) Process speed: 450 mm / sec The above evaluation images were printed 100,000 times to assess cleaning performance. When cleaning failures occurred, vertical streaks of dirt appeared on the surface of the electrostatic roller and on the paper. Visual evaluation of this condition was used as an indicator for evaluating cleaning performance. A: No vertical streaks on the paper, and no dirt on the electrostatic roller. B: No vertical streaks on the paper, but there is some dirt on the electrostatic roller. C: One vertical streak appears on the paper. D: Two to five vertical lines appear on the paper. E: More than 5 vertical lines appear on the paper. In the above evaluation criteria, A to C were defined as acceptable levels in the present invention, D as the level of the prior art, and E as an unacceptable level in the present invention. The results are shown in Table 6.

[0246] <Evaluation of Ghost Occurrence> The occurrence of ghosts was evaluated as follows.

[0247] In the modified imageRUNNER ADVANCE C5560, the mechanism for discharging excess magnetic carriers from the developer unit was removed. Paper: CS-680 (68.0g / m 2 )

[0248] The amount of toner transferred to the paper in a FFH image (solid color image) is 0.45 mg / cm². 2 The image forming apparatus was adjusted to achieve this result.

[0249] Next, 999 test charts, each with solid black vertical stripes and solid white areas as shown in Figure 2, were fed through the machine consecutively. Then, the 1000th chart was printed in the same job, resulting in a full-screen halftone image. The paper feeding direction is shown in Figure 2. On the halftone image, the image density of the areas where solid black vertical stripes were fed (a) and the areas where solid white was fed (b) was measured, and the occurrence of ghosting was evaluated based on the difference in density. Figure 4 shows the case where ghosting occurred.

[0250] Image density was measured using an X-Rite color reflectance densitometer (X-rite 500 Series, manufactured by X-rite). Measurements were taken under normal temperature and humidity (NN) conditions (temperature 23°C, relative humidity 50% to 60%), normal temperature and low humidity (NL) conditions (temperature 23°C, relative humidity 5%), and high temperature and high humidity (HH) conditions (temperature 30°C, relative humidity 80%). The value with the highest density difference was used as the density difference and evaluated according to the following criteria.

[0251] (Evaluation criteria: Ghost) A: The concentration difference between region (a) and region (b) is less than 0.015. B: The concentration difference between region (a) and region (b) is 0.015 or greater and less than 0.030. C: The concentration difference between region (a) and region (b) is 0.030 or greater and less than 0.045. D: The concentration difference between region (a) and region (b) is 0.45 or greater and less than 0.060. E: The concentration difference between region (a) and region (b) is 0.06 or greater. In the above evaluation criteria, A to C were defined as acceptable levels in the present invention, D as the level of the prior art, and E as an unacceptable level in the present invention. The results are shown in Table 6.

[0252] Furthermore, the rank in each evaluation was scored as follows, and the sum of these scores was used as the overall score. A total score of 11 points or higher indicated that the effects of the present invention were realized.

[0253] [Examples 2-21, Comparative Examples 1-4] Two-component developers 2-25 were evaluated in the same manner as developer 1. The results are shown in Table 6.

[0254] [Table 6] [Explanation of symbols]

[0255] 1. Raw material quantitative supply means, 2. Compressed gas flow rate adjustment means, 3. Inlet pipe, 4. Protruding member, 5. Supply pipe, 6. Processing chamber, 7. Hot air supply means, 8. Cold air supply means, 9. Regulating means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distribution member, 13. Swirling member, 14. Powder particle supply port

Claims

1. A toner having toner particles and an external additive, The external additive contains composite particles having organosilicon polymer particles and inorganic particles present on the surface of the organosilicon polymer particles. In the surface image of the composite particle obtained by surface observation using a scanning electron microscope, three or more inorganic particles are present in the surface image of one composite particle. When a luminance histogram is created for the composite particle surface observation using a scanning electron microscope, the luminance histogram includes, (i) Peak A including the low-luminance maximum P1, (ii) Peak B including the high-luminance maximum value P2, and (iii) The local minimum value V between P1 and P2, There exists, Peak A is a peak originating from the organosilicon polymer particles, and peak B is a peak originating from the inorganic particles. In the luminance histogram, peak A and peak B are separated by the minimum value V as the boundary, and when the area of ​​peak A is S1 and the area of ​​peak B is S2, 0.68≧S2 / (S1+S2)≧0.10 A toner characterized by satisfying the following conditions.

2. The toner according to claim 1, wherein the number-average particle size of the inorganic particles is 5 nm or more and 60 nm or less.

3. The toner according to claim 1 or 2, wherein the composite particles have an SF-1 of 108 or less and an SF-2 of 225 or more and 400 or less.

4. The toner according to any one of claims 1 to 3, wherein the composite particles are contained in an amount of 0.3 parts by mass or more per 100 parts by mass of the toner particles.

5. The toner according to any one of claims 1 to 4, wherein the organosilicon polymer particles are polyorganosilsesquioxane particles.

6. The toner according to any one of claims 1 to 5, wherein the inorganic particles are silica particles.

7. When the number-average particle size of the organosilicon polymer particles is R1 and the number-average particle size of the inorganic particles is R2, 0.10 ≤ R² / R¹ ≤ 0.40 The toner according to any one of claims 1 to 6 that satisfies the requirements.

8. The toner according to any one of claims 1 to 7, wherein the external additive comprises silica fine powder having a density of 0.87 or less.

9. A method for manufacturing toner according to any one of claims 1 to 8, A composite particle forming step of mixing the organosilicon polymer particles and the inorganic particles to form the composite particles, After the composite particle formation step, the composite particles and the toner particles are mixed in an external addition step in which the composite particles are added to the toner particles. A method for manufacturing toner, characterized by including [the specified ingredient / feature].

10. A method for producing toner according to claim 9, comprising an oil treatment step of applying oil treatment to the inorganic particles before the composite particle formation step.

11. A method for producing toner according to claim 9 or 10, comprising a fatty acid treatment step of subjecting the organosilicon polymer particles to fatty acid treatment before the composite particle formation step.

12. A method for producing toner according to any one of claims 9 to 11, further comprising a heat treatment step of heat-treating the surface of the toner particles to which the composite particles have been added after the external addition step.

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