JP6270467B2 - toner - Google Patents

Description

  The present invention relates to a toner used for electrophotography and the like.

In recent years, copiers or printers using electrophotography have become increasingly demanded for low cost and small size in addition to high speed and high image quality. In other words, it is required to maintain high image quality even when designed with simpler components, and even for long-term use. To achieve high image quality, the toner must be more fluid than before. . From such a background, studies for increasing the fluidity of toner are being actively conducted.
Therefore, Patent Document 1 discloses a toner using small particle size silica particles as an additive. However, a toner containing many additives having a small particle size has a problem of poor cleaning due to too good fluidity.
Patent Document 2 discloses a toner using silica particles having a large particle size as an additive for the purpose of ensuring cleaning properties. However, a toner containing an additive having a large particle size is feared to have a decrease in fluidity, and thus it is necessary to use a large amount of the additive having a large particle size. A toner containing a large amount of an additive having a large particle size tends to increase the amount of free additives, and there is a concern that image defects due to the free additives may occur.

JP 2008-151893 A JP2013-120230A

  An object of the present invention is to provide a toner that is excellent in cleaning property and satisfies high image quality even in a toner to which inorganic fine particles having a small particle diameter are added.

That is, the present invention relates to a toner having toner particles containing a binder resin and inorganic fine particles, and the toner contains 1.5 parts by mass or more of the inorganic fine particles with respect to 100.0 parts by mass of the toner particles. The content of inorganic fine particles having a particle size of 30 nm or less in the inorganic fine particles is 80% by mass or more, and the tap density of the toner is 0.62 g / cm ³ or more and 0.68 g / cm. ³ or less, and the toner has an Et 100 of 200 mJ or more and 350 mJ or less.
(However, Et100 (mJ) is a powder fluidity analyzer that allows the peripheral speed of the outermost edge of the propeller-type blade to rotate vertically at 100 mm / sec so as to vertically enter the toner powder layer in the container. (Measurement is started from the position of 100 mm from the bottom of the layer, and represents the sum of the rotational torque and the vertical load obtained when entering from the bottom to the position of 10 mm.)

  According to the present invention, it is possible to obtain a toner excellent in cleaning properties and satisfying high image quality even in a toner to which inorganic fine particles having a small particle diameter are added.

It is a schematic diagram which shows an example of the mixing processing apparatus which can be used for the external addition mixing of inorganic fine particles. It is a schematic diagram which shows an example of a structure of the stirring member used for a mixing processing apparatus. It is explanatory drawing of the external appearance (a) of the propeller-type blade of a powder fluidity | liquidity analyzer, and the twist angle (b) of a blade outermost edge part.

The inventors of the present invention have intensively studied toners that can improve the above problems. In particular, in a toner to which inorganic fine particles having a small particle diameter are added, the above effect is exhibited very effectively by controlling the total density of the rotational torque and the vertical load measured by the toner tap density and the powder flowability analyzer. As a result, the present invention was reached.
In the present invention, in a toner having toner particles containing a binder resin and inorganic fine particles, the toner contains 1.5 parts by mass or more of the inorganic fine particles with respect to 100.0 parts by mass of the toner particles. 0 parts by weight contain less content of a particle diameter 30nm or less of the inorganic fine particles in the inorganic fine particles is 80 mass% or more, the tap density of the toner is, 0.62 g / cm ³ or more 0.68 g / cm ³ or less The Et100 of the toner is 200 mJ or more and 350 mJ or less.
(However, Et100 (mJ) is a powder fluidity analyzer that allows the peripheral speed of the outermost edge of the propeller-type blade to rotate vertically at 100 mm / sec so as to vertically enter the toner powder layer in the container. (Measurement is started from the position of 100 mm from the bottom of the layer, and represents the sum of the rotational torque and the vertical load obtained when entering from the bottom to the position of 10 mm.)

The reason why the above problems have been solved in the present invention is estimated as follows.
This shows that the toner tap density is larger, so that the toner is more easily packed, and such a toner is likely to form a blocking layer at the cleaning blade portion for cleaning. When the tap density is less than 0.62 g / cm ³ , in a low-temperature environment, a high-circularity toner containing inorganic fine particles having a small particle diameter cannot form a sufficient blocking layer, resulting in poor cleaning. On the other hand, when it exceeds 0.68 g / cm ³ , it is in an overtightened state in the container filled with toner. In particular, when a high-printing image is printed after being left to stand and is restarted, a toner supply failure occurs, and a solid image follow-up failure occurs. A more preferable range of tap density is 0.64 g / cm ³ or more and 0.66 g / cm ³ or less. The tap density can be controlled by the amount of inorganic fine particles having a small particle diameter, particularly the amount of inorganic fine particles having a size of 10 nm or less.

In addition, the smaller the Et100 is, the easier it is to loosen, and since such a toner loosens the blocking layer formed at the cleaning blade part when the printer is restarted, the friction between the photosensitive member and the toner on the blocking layer. Is reduced. When Et100 exceeds 350 mJ, friction between the photosensitive member and the toner on the blocking layer increases when the printer is restarted, and the toner moves in the rotational direction of the photosensitive member, so that the toner passes through the cleaning blade, resulting in poor cleaning. On the other hand, when Et100 is less than 200 mJ, the blocking layer of the cleaning blade is loosened and collapses when the printer is restarted, resulting in poor cleaning. A preferable range of Et100 is 250 mJ or more and 350 mJ or less. Et100 can be controlled by the amount of silica fine particle treatment agent such as silicone oil added.
In addition, it is considered that the tap density and Et100 as described above can be achieved by adding small-sized inorganic fine particles more uniformly and further to the toner particles so as not to be embedded too much. In general, a toner with a high degree of circularity is inferior in cleaning properties, but in the present invention, a sufficient effect can be obtained even with a toner with a high degree of circularity.

Next, a toner manufacturing method will be described.
The toner particles used in the present invention may be produced by any method, but production by granulation in an aqueous medium such as suspension polymerization, emulsion polymerization, and suspension granulation. Preferably, it is manufactured by the method. In the present invention, the average circularity of the toner is preferably 0.970 or more, and the transferability is further improved. The average circularity is more preferably 0.975 or more. The average circularity can be controlled by the polymerization temperature at the time of toner particle production.
Hereinafter, a method for producing toner particles will be described by exemplifying a suspension polymerization method suitable for obtaining toner particles used in the present invention. The binder resin and, if necessary, the colorant, wax and other additives are uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser, and polymerized therein. An initiator is dissolved to prepare a polymerizable monomer composition. Next, toner particles are manufactured by suspending the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer and performing polymerization. The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer composition, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

As the binder resin used in the toner of the present invention, a vinyl copolymer composed of a styrene resin and an acrylic resin, a polyester resin, or the like can be used. The use of a copolymer is preferable because the development stability is further enhanced.
Among vinyl resins, acrylic resins and copolymers with acrylic resins based on styrene resins are preferred.

The following are mentioned as a polymerizable monomer for producing | generating a binder resin.
Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene or m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid Propyl, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-acrylate Acrylic ester monomers such as ethylhexyl, 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, or diethylaminoethyl methacrylate Methacrylic acid ester monomer.

In the production of the toner of the present invention, a crosslinking agent may be used during the synthesis of the binder resin as a means for controlling the molecular weight of the binder resin component.
Examples of the crosslinking agent used in the present invention include the following as the bifunctional crosslinking agent.
Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku) or the above diacrylate instead of dimethacrylate Thing.

The following are mentioned as a polyfunctional crosslinking agent.
Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate or triallyl trimellitate.
The addition amount of these crosslinking agents is preferably 0.01 parts by mass or more and 10.00 parts by mass or less, more preferably 0.10 parts by mass or more and 5.10 parts by mass or more with respect to 100.00 parts by mass of the polymerizable monomer. 00 parts by mass or less.

The following are mentioned as a polymerization initiator used for the toner of the present invention.
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile or azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t- Butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, or lauroyl Peroxide-based polymerization initiator such as peroxide.

In the toner of the present invention, a known chain transfer agent, polymerization inhibitor and the like can be further added in order to control the degree of polymerization of the polymerizable monomer constituting the binder resin.
In the toner of the present invention, a polar resin such as a polyester resin can be used together with the above-described binder resin. In particular, when toner particles are produced by a suspension polymerization method, if a polar resin is added to the polymerizable monomer composition, a thin layer can be formed on the surface of the toner particles by the polar resin. That is, adding a polar resin can reinforce the shell portion of the core-shell structure.
The addition amount of the polar resin is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 2 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a charge control agent can be added as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.
As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable.
Examples of the charge control agent that control the toner to be negatively charged include the following.
Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol. Urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, resin-based charge control agents.

Examples of the charge control agent that controls the toner to be positively charged include the following.
Nigrosine-modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent.
In the toner of the present invention, these charge control agents may be used alone or in combination of two or more.
The blending amount of the charge control agent is preferably 0.1 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin. Or less. However, it is not essential to add a charge control agent to the toner of the present invention, and it is not always necessary to include the charge control agent in the toner by actively utilizing frictional charging with the toner regulating member or the toner carrier. Absent.

The toner of the present invention preferably contains a colorant in order to impart coloring power. Examples of the colorant used in the toner of the present invention include the following organic pigments, organic dyes, and inorganic pigments.
Examples of the organic pigment or organic dye as the cyan colorant include a copper phthalocyanine compound or a derivative thereof, an anthraquinone compound, or a basic dye lake compound. Specific examples include the following.
C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

Examples of organic pigments or organic dyes as magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, or perylene compounds. It is done. Specific examples include the following.
C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 254, C.I. I. Pigment Red 282.

Examples of the organic pigment or organic dye as the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following.
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I
. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black or those prepared by using the above yellow colorant / magenta colorant / cyan colorant to black.
These colorants can be used alone or in combination. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the binder resin.

The toner of the present invention may further contain a wax. Specifically, the following: monofunctional ester waxes represented by behenyl behenate, stearyl stearate, palmitic acid palmitate, etc .; difunctional ester waxes represented by dibehenyl sebacate, hexanediol dibehenate, etc .; Trifunctional ester waxes represented by glycerin tribehenate; tetrafunctional ester waxes represented by pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, etc .; dipentaerythritol hexastearate, dipentaerythritol hexapalmi Hexafunctional ester waxes typified by Tate and the like; Multifunctional ester waxes typified by polyglycerin behenate; Natural ester waxes typified by carnauba wax and rice wax; Petroleum waxes such as raffin wax, microcrystalline wax, petrolatum and their derivatives; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and their derivatives such as polyethylene wax and polypropylene wax; higher aliphatic alcohols; stearic acid, palmitic acid Fatty acids such as acids; acid amide waxes and the like.
The wax is preferably used in an amount of 1.0 to 30.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

When the toner particles used in the present invention are granulated in an aqueous medium, known dispersion stabilizers and organic dispersion stabilizers can be used as the dispersion stabilizer used in preparing the aqueous medium. The slightly water-soluble dispersion stabilizer is preferable, and it is preferable to use a slightly water-soluble inorganic dispersion stabilizer that is soluble in acid.
Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer.
Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, or alumina. Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, or starch.

Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following.
Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, or calcium oleate.
When preparing an aqueous medium in which the above dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. Further, in order to obtain a dispersion stabilizer particle having a fine uniform particle size, an aqueous medium may be prepared by generating a dispersion stabilizer in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

The toner of the present invention is a toner having toner particles and external additives such as inorganic fine particles. In the present invention, the content of inorganic fine particles having a particle size of 30 nm or less in the inorganic fine particles is 80% by mass or more. The inorganic fine particles are used by adding 1.5 parts by weight or more and 3.0 parts by weight or less, preferably 1.5 parts by weight or more and 2.5 parts by weight or less, with respect to 100.0 parts by weight of the toner particles. is there.
Examples of the inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable. Examples of external additives other than inorganic fine particles include various resin particles and fatty acid metal salts. These are preferably used alone or in combination.

Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, wet silica produced from water glass, and sol-gel silica produced by a sol-gel method. As the inorganic fine particles, dry silica having less silanol groups on the surface and inside the silica fine particles and less Na ₂ O and SO ₃ ²⁻ is more preferable. The dry silica may be composite fine particles of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.

Since the inorganic fine particles can be hydrophobized to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics under a high humidity environment, it is preferable to use the hydrophobized inorganic fine particles. . When the inorganic fine particles added to the toner absorb moisture, the charge amount as the toner is lowered, the developing property and the transfer property are easily lowered, and the durability tends to be lowered.
Examples of the hydrophobic treatment agent for inorganic fine particles include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. Can be mentioned. These treatment agents may be used alone or in combination.

Subsequently, a preferred example of the treatment of silica fine particles preferably used for the toner of the present invention will be described.
In the present invention, the silica fine particles are preferably silica fine particles obtained by treating the raw silica fine particles with at least silicone oil and then treating with the silane or silazane compound. Transferability, charging stability in a high temperature and high humidity environment, and fluidity after high temperature storage can be achieved at a higher level.
The silica fine particles are more preferably those obtained by crushing the raw silica fine particles after treating them with silicone oil. By performing the crushing treatment, the fluidity of the toner is further enhanced.

Furthermore, in the present invention, the silica fine particle is preferably 0.50% by mass or less, and 0.10% by mass or less, in the silica fine particle surface-treated with silicone oil, using hexane. More preferably. In this case, reduction of free oil in high-temperature storage can be expected, fluidity after high-temperature storage is good, and solid image followability is good.
The amount of the extracted silicone oil can be appropriately controlled according to the amount of treatment and the treatment temperature when the raw silica fine particles are treated with the silicone oil.

Furthermore, in the present invention, the hydrophobicity of the silica fine particles is preferably 95% or more and 100% or less, and more preferably 97% or more and 100% or less. When the hydrophobization rate of the silica fine particles is 95% or more, the charging stability during storage in a high temperature and high humidity environment is further improved. The hydrophobization rate of the silica fine particles can be controlled by the treatment amount and treatment conditions of the silane or silazane compound.
As the silicone oil used for the treatment of the silica fine particles of the present invention, a known silicone oil can be used without particular limitation, but straight silicone is particularly preferable.
More specifically, for example, dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, or methylhydrogen silicone oil can be used.
The method for treating the silicone oil may be, for example, mixing silica fine particles and silicone oil directly using a mixer such as a Henschel mixer, or may be a method of stirring the raw silica fine particles while spraying the silicone oil. Alternatively, it may be prepared by dissolving or dispersing silicone oil in an appropriate solvent (preferably adjusted to pH 4 with an organic acid or the like), mixing with the raw silica fine particles, and then removing the solvent. In addition, put the silica fine particles into the reaction vessel, add alcohol water while stirring under a nitrogen atmosphere, introduce a silicone oil treatment liquid into the reaction vessel to perform surface treatment, and then heat and stir to remove the solvent. You may take the method to do.

As the silane or silazane compound used for the treatment of the silica fine particles of the present invention, a known silane or silazane compound can be used without particular limitation.
Specifically, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchloro. Silane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, or diphenyl Examples include diethoxysilane. Among these, hexamethyldisilazane is preferably used from the viewpoint of processing uniformity and coupling bond reliability. Silane compounds or silazane compounds can be used alone or in combination of two or more.

The treatment with at least one of the silane or silazane compound necessary for obtaining the silica fine particles of the present invention is a dry treatment in which the vaporized silane or silazane compound is reacted with the raw silica fine particles made into a cloud by stirring, or the raw material It can be processed by a generally known method such as a wet method in which silica fine particles are dispersed in a solvent and a silane or silazane compound is dropped.
In the present invention, when treating with a silane compound or a silazane compound, the total amount of the silane compound or the silazane compound is 100 parts by mass or less than 50 parts by mass with respect to 100 parts by mass of the raw silica fine particles or 100 parts by mass of the titanium oxide fine particles. Good.

As a mixing processing apparatus for externally adding and mixing the inorganic fine particles (hereinafter also referred to as external mixing), a known mixing processing apparatus can be used, but the tap density and Et100 of the present invention can be easily controlled. In view of this, an apparatus as shown in FIG. 1 is preferable.
FIG. 1 is a schematic view showing an example of a mixing treatment apparatus that can be used when externally adding and mixing inorganic fine particles used in the present invention.
The mixing device is configured to take a share in a narrow clearance portion with respect to the toner particles and the inorganic fine particles, so that the inorganic fine particles adhere to the toner particle surface while loosening the secondary fine particles from the primary particles to the primary particles. Can be made.
Further, as will be described later, the tap density and Et100 are controlled within the preferable ranges in the present invention in that the toner particles and the inorganic fine particles are easily circulated in the axial direction of the rotating body and are sufficiently mixed uniformly before the fixing proceeds. It's easy to do.

On the other hand, FIG. 2 is a schematic diagram showing an example of a configuration of a stirring member used in the mixing processing apparatus.
Hereafter, the external addition mixing process of the said inorganic fine particle is demonstrated using FIG.1 and FIG.2.
The mixing processing apparatus for externally mixing the inorganic fine particles has a rotating body 2 having at least a plurality of stirring members 3 installed on the surface, a drive unit 8 that rotationally drives the rotating body, and a gap between the stirring member 3 and the rotating member 2. The main body casing 1 is provided.

The clearance (clearance) between the inner peripheral portion of the main body casing 1 and the stirring member 3 gives a uniform share to the toner particles and easily adheres to the toner particle surface while loosening the inorganic fine particles from the secondary particles to the primary particles. Therefore, it is preferable to keep it constant and minute.
Further, in this apparatus, the diameter of the inner peripheral portion of the main body casing 1 is not more than twice the diameter of the outer peripheral portion of the rotating body 2. In FIG. 1, an example in which the diameter of the inner peripheral portion of the main casing 1 is 1.7 times the diameter of the outer peripheral portion of the rotating body 2 (the diameter of the body portion obtained by removing the stirring member 3 from the rotating body 2). If the diameter of the inner peripheral portion of the main body casing 1 is less than or equal to twice the diameter of the outer peripheral portion of the rotating body 2, the processing space in which the force acts on the toner particles is appropriately limited. A sufficient impact force is applied to the inorganic fine particles.

Moreover, it is preferable to adjust the said clearance according to the magnitude | size of a main body casing. It is preferable that the diameter of the inner peripheral portion of the main body casing 1 is about 1% or more and 5% or less in that a sufficient share is applied to the inorganic fine particles. Specifically, when the diameter of the inner peripheral part of the main body casing 1 is about 130 mm, the clearance is about 2 mm or more and about 5 mm or less. When the diameter of the inner peripheral part of the main body casing 1 is about 800 mm, the clearance is about 10 mm or more and 30 mm or less. It should be about.
In the external addition mixing process of the inorganic fine particles in the present invention, the rotating body 2 is rotated by the drive unit 8 using the mixing processing device, and the toner particles and the inorganic fine particles charged into the mixing processing device are stirred and mixed. Inorganic fine particles are externally mixed on the surface of the toner particles.
As shown in FIG. 2, at least a part of the plurality of stirring members 3 is formed as a feeding stirring member 3 a that sends toner particles and inorganic fine particles in one axial direction of the rotating body as the rotating body 2 rotates. Is done. At least a part of the plurality of stirring members 3 is formed as a return stirring member 3b that returns the toner particles and the inorganic fine particles to the other direction in the axial direction of the rotating body 2 as the rotating body 2 rotates.

Here, when the raw material inlet 5 and the product outlet 6 are provided at both ends of the main casing 1 as shown in FIG. 1, the direction from the raw material inlet 5 toward the product outlet 6 (in FIG. 1). (Right direction) is called “feed direction”.
That is, as shown in FIG. 2, the plate surface of the feeding stirring member 3a is inclined so as to feed the toner particles in the feeding direction (13). On the other hand, the plate surface of the stirring member 3b is inclined so as to send toner particles and inorganic fine particles in the return direction (12).
Thus, the external addition mixing process of the inorganic fine particles is performed on the surface of the toner particles while repeatedly performing the feed (13) in the “feed direction” and the feed (12) in the “return direction”.
The stirring members 3a and 3b are a set of a plurality of members arranged at intervals in the circumferential direction of the rotating body 2. In the example shown in FIG. 2, the stirring members 3a and 3b form a pair of two members on the rotating body 2 at an interval of 180 degrees, but three members at an interval of 120 degrees or an interval of 90 degrees. It is good also as a set of many members, such as four sheets.

In the example shown in FIG. 2, a total of 12 stirring members 3a and 3b are formed at equal intervals.
Further, in FIG. 2, D indicates the width of the stirring member, and d indicates the interval indicating the overlapping portion of the stirring member. From the viewpoint of efficiently feeding toner particles and inorganic fine particles in the feeding direction and the returning direction, it is preferable that D has a width of about 20% to 30% with respect to the length of the rotating body 2 in FIG. FIG. 2 shows an example of 23%. Furthermore, it is preferable that the stirring members 3a and 3b have some overlap d between the stirring member 3b and the stirring member when an extension line is drawn in the vertical direction from the end position of the stirring member 3a. Thereby, it is possible to efficiently share the inorganic fine particles which are secondary particles. D is preferably 10% or more and 30% or less in terms of applying a share.
Regarding the shape of the blade, in addition to the shape shown in FIG. 2, if the toner particles can be sent in the feeding direction and the returning direction and the clearance can be maintained, the shape having a curved surface and the tip blade portion are A paddle structure coupled to the rotating body 2 with a rod-like arm may be used.

Hereinafter, the present invention will be described in more detail with reference to the schematic views of the apparatus shown in FIGS.
The apparatus shown in FIG. 1 includes a rotating body 2 having at least a plurality of stirring members 3 installed on a surface thereof, a drive unit 8 that rotationally drives the rotating body 2, and a main casing provided with a gap between the stirring member 3 and the main body casing. 1 and a jacket 4 on the inner side of the main body casing 1 and the side surface 10 of the rotating body end, through which a cooling medium can flow.
Further, the apparatus shown in FIG. 1 is used to discharge toner from the main casing 1 and the raw material inlet 5 formed in the upper portion of the main casing 1 and the externally added and mixed toner to introduce toner particles and inorganic fine particles. In addition, a product discharge port 6 formed in the lower part of the main body casing 1 is provided.
Further, in the apparatus shown in FIG. 1, a raw material inlet inner piece 16 is inserted into the raw material inlet 5, and a product outlet inner piece 17 is inserted into the product outlet 6.

In the present invention, first, the raw material inlet inner piece 16 is taken out from the raw material inlet 5, and the toner particles are put into the processing space 9 from the raw material inlet 5. Next, inorganic fine particles are introduced into the treatment space 9 from the raw material inlet 5 and the inner piece 16 for raw material inlet is inserted. Next, the rotating body 2 is rotated by the drive unit 8 (11 indicates the direction of rotation), and the processed material introduced above is externally added while being stirred and mixed by a plurality of stirring members 3 provided on the surface of the rotating body 2. Mix.
The order of charging may be such that the inorganic fine particles are first charged from the raw material charging port 5 and then the toner particles are charged from the raw material charging port 5. Further, after the toner particles and the inorganic fine particles are mixed in advance by a mixer such as a Henschel mixer, the mixture may be supplied from the raw material input port 5 of the apparatus shown in FIG.
Although it does not specifically limit as processing time, Preferably it is 3 minutes or more and 10 minutes or less.
Although the rotation speed of the stirring member at the time of external mixing is not particularly limited, the shape of the stirring member 3 in the apparatus in which the volume of the processing space 9 of the apparatus shown in FIG. 1 is 2.0 × 10 ⁻³ m ³ is shown in FIG. The rotation speed of the stirring member when it is made is preferably 800 rpm or more and 2500 rpm or less.
After completion of the external addition mixing process, the product discharge port inner piece 17 is taken out from the product discharge port 6, the rotating body 2 is rotated by the drive unit 8, and the toner is discharged from the product discharge port 6. From the obtained toner, coarse particles and the like are separated by a sieve such as a circular vibratory sieve as needed to obtain a toner.

Hereinafter, the measuring method according to the present invention will be described.
<Tap density measurement>
The tap density is measured by the following method using a powder tester (manufactured by Hosokawa Micron).
A cylindrical cap having a diameter of 5.03 cm, a height of 5.03 cm, and a volume of 100 cm ³ is fitted with a cylindrical cap, and powder is added to this upper edge, and tapping with a tap height of 1.8 cm is performed 180 times. After completion, the cap is removed, the powder is ground on the upper surface of the container and weighed, and the density in this state is defined as the tap density (g / cm ³ ).

<Et100 (mJ) measurement>
Et100 (mJ) in the present invention is “powder fluidity analyzer powder rheometer FT.
4 ”(manufactured by Freeman Technology, hereinafter may be abbreviated as FT4).
Specifically, the measurement is performed by the following operation.
As the propeller type blade, a 48 mm diameter blade (see FIG. 3, model number: C210, material: SUS, hereinafter may be abbreviated as “blade”) dedicated to FT4 is used. This propeller-type blade has a rotation axis in the normal direction at the center of a 48 mm × 10 mm blade plate, and the blade plate has an outermost edge portion (24 mm portion from the rotation shaft) of 70 ° and a portion 12 mm from the rotation shaft. It is smoothly twisted counterclockwise, such as 35 °.
As the measurement container, a cylindrical split container dedicated to FT4 (model number: C203, material: glass, diameter 50 mm, volume 160 ml, height 82 mm from the bottom surface to the split part, hereinafter may be abbreviated as container) is used. .
In addition, 100 g of toner left in an environment of a temperature of 23 ° C. and a humidity of 60% RH for 3 days or more is put in the measurement container to form a toner powder layer.

(1) Conditioning operation (a) A propeller blade is rotated clockwise with respect to the powder layer surface so that the peripheral speed of the outermost edge of the blade is 60 mm / sec (the powder layer is loosened by the rotation of the blade). Direction). The surface of the powder layer at an approach speed at which the angle between the locus drawn by the outermost edge of the moving blade and the surface of the powder layer (hereinafter sometimes referred to as the angle formed) is 5 °. From the bottom surface of the toner powder layer to the position of 10 mm in the vertical direction. Thereafter, the toner powder layer is rotated while rotating clockwise with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 60 mm / sec. The blade is advanced to a position of 1 mm from the bottom surface. Further, while rotating clockwise with respect to the powder layer surface so that the angle formed is 5 ° and the peripheral speed of the outermost edge of the blade is 60 mm / sec, 100 mm from the bottom surface of the toner powder layer. Move the blade to position and remove it. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(B) The operations (1) to (a) are repeated five times to remove the air taken in the toner powder layer.

(2) Split operation The conditioned powder layer or compressed powder layer is cut off at the split portion of the FT4 container described above, and the toner on the upper part of the powder layer is removed. By this operation, the volume of the toner powder layer can be made the same for each measurement.
(3) Measurement operation (i) Et100 measurement (a) Conditioning operation similar to (1)-(a) is performed once.
(B) Rotate the propeller blade counterclockwise with respect to the powder layer surface (direction in which the powder layer is pushed in by rotation of the blade) so that the peripheral speed of the outermost edge of the blade is 100 mm / sec. To do. The blade is advanced in the vertical direction from the powder layer surface to a position 10 mm from the bottom surface of the toner powder layer at an approach speed of 5 °. Thereafter, the blade rotates clockwise with respect to the surface of the powder layer so that the peripheral speed of the outermost edge of the blade is 60 mm / sec, and the angle forming the vertical entry speed to the powder layer becomes 2 °. It is made to approach to the position of 1 mm from the bottom face of the powder layer at the approach speed. Further, the blade is moved to a position of 100 mm from the bottom surface of the powder layer at a speed of 5 °, and is extracted. When the extraction is completed, the toner attached to the blade is wiped off by rotating the blade alternately in small clockwise and counterclockwise directions.
(C) The operations of (3)-(i)-(b) are repeated six more times, and the rotation obtained when the blade enters the position from 100 mm to 10 mm from the bottom of the toner powder layer in the seventh time. The total Et of the torque and the vertical load is Et100.

<Average circularity measurement>
The average circularity of the toner is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.
In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Measurement of amount of extracted silicone oil>
The amount of silica oil extracted from silica fine particles is measured as follows. 1.0 g of silica fine particles is weighed into a 50 ml screw tube, and 20 ml of normal hexane is added. Then, it extracts for 10 minutes with the intensity | strength 20 (output 10W) with an ultrasonic homogenizer (VP-050 by TAITEC). The obtained extract is separated with a centrifuge to obtain a supernatant. 10 g of the obtained supernatant is dried with an evaporator, the residue is made into silicone oil, the silicone oil concentration in the supernatant is calculated, and the amount of extracted silicone oil (the amount of extracted silicone oil in silica fine particles [mass%]) is obtained.

<Measurement of hydrophobicity>
The hydrophobicity of silica fine particles is measured as follows. First, 1 g of silica fine particles is weighed into a separating funnel (200 ml), 100 ml of pure water is added thereto, stoppered, shaken with a tumbler mixer (T2F manufactured by Shinmaru Enterprises Co., Ltd.) for 10 minutes, and then allowed to stand for 10 minutes. Put. Thereafter, 20 to 30 ml of the lower layer was extracted from the funnel, and then the lower layer mixed solution was separated into a 10 mm quartz cell and applied to a colorimeter using pure water as a blank, and the 500 nm passage rate (%) was determined as the hydrophobicity ( %).

<Measurement of particle size of inorganic fine particles>
The primary particle size of the inorganic fine particles was measured by adding 1 part by mass of inorganic fine particles to 100 parts by mass of toner particles, using a field emission scanning electron microscope (FE-SEM) (S-4800) (Hitachi Co., Ltd.). A photograph of the surface of the toner particles magnified 100,000 times by Hi-Technologies) was taken, and the particle size of 100 or more inorganic fine particles was measured using the enlarged photograph. When the shape is spherical, the absolute maximum length is counted, and when the shape has a major axis and a minor axis, the major axis is counted as a particle diameter.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. In the examples and comparative examples, all parts and% are based on mass unless otherwise specified.

<Production Example of Silica Fine Particle 1>
As a first treatment step, 10 parts by mass of dimethyl silicone oil (viscosity = 100 mm ² / s) with respect to 100 parts by mass of fumed silica (specific surface area 380 m ² / g by BET method, number average particle diameter of primary particles 7 nm). Was sprayed and stirring was continued for 30 minutes. Thereafter, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours, whereby dimethyl silicone oil was baked on the fumed silica surface to complete the reaction.
As the second treatment step, 40 parts by mass of hexamethyldisilazane (hereinafter also referred to as HMDS) was sprayed on the silica fine particles produced in the first treatment step, and the silane compound treatment was performed in a fluidized state of silica. . This reaction was continued for 60 minutes, and then the reaction was terminated. After completion of the reaction, crushing was performed with a pulverizer (manufactured by Hosokawa Micron Corporation) to obtain silica fine particles 1. Table 1 shows the physical properties of the silica fine particles 1 obtained.

<Production example of silica fine particles 2 to 5>
In the production example of silica fine particles 1, silica fine particles 2 to 5 were obtained in the same manner as in the production example of silica fine particles 1 except that the amount of the treating agent was changed to the amount described in Table 1. The physical properties of the obtained silica fine particles 2 to 5 are shown in Table 1.

<Example of production of titanium oxide fine particles 1>
As a first treatment step, 10 parts by mass of isobutyltrimethoxysilane was sprayed on the inside with respect to 100 parts by mass of titanium oxide fine particles having a number average particle diameter of 15 nm of primary particles, and a silane compound treatment was performed in a fluidized state of titanium. . This reaction was continued for 60 minutes, and then the reaction was terminated.
As a 2nd process process, 10 mass parts dimethyl silicone oil was sprayed with respect to the titanium fine particle produced | generated by the 1st process process, and stirring was continued for 30 minutes. Thereafter, the temperature was raised to 190 ° C. with stirring, and the mixture was further stirred for 3 hours, whereby dimethyl silicone oil was baked on the titanium oxide surface to complete the reaction. Thereafter, crushing treatment was repeatedly performed with a jet mill until the aggregate of titanium oxide disappeared, and titanium oxide fine particles 1 were obtained. The amount of fine particles having a particle size of 30 nm or less of the obtained titanium oxide fine particles 1 was 100% by mass.

<Example of production of titanium oxide fine particles 2>
In the production example of the titanium oxide fine particles 1, titanium oxide fine particles 2 are obtained in the same manner as in the production example of the titanium oxide fine particles 1 except that titanium oxide fine particles having a primary particle number average particle size of 80 nm are used as titanium oxide before treatment. It was. The amount of fine particles having a particle size of 30 nm or less of the obtained titanium oxide fine particles 2 was 0% by mass.

<Production Example of Toner Particle 1>
With respect to 30.0 parts by mass of styrene, C.I. I. Pigment Blue 15: 3 (6.0 parts by mass) and a charge control agent (Bontron E88; manufactured by Orient Chemical Industry Co., Ltd.) (1.0 part by mass) were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.), and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads having a radius of 1.25 mm to prepare a pigment dispersion composition.
On the other hand, 900 parts by mass of ion-exchanged water heated to 60 ° C. and 2.5 parts by mass of tricalcium phosphate were added to a separate container, and stirred at 10,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo). An aqueous medium was obtained.
The following materials were mixed and dispersed at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
Pigment dispersion composition 37.0 parts by mass Styrene 45.0 parts by mass n-butyl acrylate 25.0 parts by mass Polyester resin (weight average molecular weight 9500, glass transition temperature 73 ° C) 5.0 parts by mass

Further, after heating to 60 ° C., 8.0 parts by mass of hydrocarbon wax (HNP-9; manufactured by Nippon Seiki Co., Ltd.) is added, and dispersed and mixed for 30 minutes. (Manufactured) 10.0 parts by mass was dissolved to prepare a polymerizable monomer composition.
The polymerizable monomer composition was charged into the aqueous medium and stirred at 10,000 rpm for 10 minutes with a TK homomixer at a temperature of 60 ° C. in a nitrogen atmosphere to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade. After reacting for 5 hours, the temperature was further raised to 85 ° C. and reacted for 2 hours. After cooling, hydrochloric acid was added to adjust the pH to 1.4 and stirred for 2 hours. The toner particles were separated by filtration, washed with water, and dried at a temperature of 40 ° C. for 48 hours to obtain toner particles 1. The weight average particle diameter (D4) of the obtained toner particles 1 was measured with a Coulter counter Multisizer 3 (manufactured by Beckman Coulter, Inc.) and found to be 6.7 μm.

<Production example of toner particles 2>
In the production example of toner particles 1, toner particles 2 were obtained in the same manner as in the production example of toner particles 1 except that the polymerization temperature was changed from 70 ° C. to 65 ° C. The obtained toner particles 2 had a weight average particle diameter (D4) of 6.7 μm.

<Production Example of Toner Particle 3>
The toner particles 1 were melt-kneaded with a biaxial extruder heated to 110 ° C., and the cooled kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner product. The obtained coarsely pulverized product was mechanically pulverized using a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd.). The resulting finely pulverized product is classified and removed at the same time by a multi-division classifier (Elbow Jet Classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect, and the surface modification device Faculty (manufactured by Hosokawa Micron) The toner particles 3 were obtained by surface modification and fine powder removal. The obtained toner particles 3 had a weight average particle diameter (D4) of 6.7 μm.

<Production Example of Toner 1>
The toner particles 1 were externally mixed using the apparatus shown in FIG.
In this embodiment, the apparatus shown in FIG. 1 uses an apparatus in which the diameter of the inner peripheral portion of the main casing 1 is 130 mm and the volume of the processing space 9 is 2.0 × 10 ⁻³ m ^3. The rated power was 5.5 kW, and the shape of the stirring member 3 was that shown in FIG. The overlapping width d of the stirring member 3a and the stirring member 3b in FIG. 2 is 0.25D with respect to the maximum width D of the stirring member 3, and the clearance between the stirring member 3 and the inner periphery of the main casing 1 is 3.0 mm. .
To the apparatus described above, 100.0 parts by mass of toner particles 1, 0.8 parts by mass of silica fine particles 1, and 0.8 parts by mass of titanium oxide fine particles 1 were charged.
Toner 1 was manufactured by externally adding and mixing the drive unit 8 at a rotational speed of 2000 rpm and a processing time of 5 minutes. Table 3 shows the physical properties of Toner 1 thus obtained.

<Production Examples of Toners 2 to 17>
Toners 1 to 17 were produced in the same manner as in Production Example of Toner 1 except that the toner particles, silica fine particles, titanium oxide fine particles, external addition mixing apparatus, and external addition mixing conditions shown in Table 2 were changed. Table 3 shows the physical properties of the obtained toners 2 to 17. In addition, when using a Henschel mixer as an external addition mixing apparatus, Henschel mixer FM10C (made by Mitsui Miike Chemical Industries Co., Ltd.) was used.

[Example 1]
LBP9200C (manufactured by Canon Inc.) was used as an evaluation machine, and toner 1 was refilled in a cyan cartridge. The cleaning property was evaluated in a 0 ° C. environment, and the solid followability (toner supply property) and cleaning property after standing in a low temperature and low humidity environment (15 ° C., 10% RH) were evaluated. In addition, after storing the cartridge in a high temperature and high humidity storage environment (40 ° C./95% RH) for 30 days, in a high temperature and high humidity environment (30 ° C./80% RH), transferability, solid followability (fluidity), fog (charging) (Stability) was evaluated. For the evaluation paper, Canon Office 70 (basis weight 70 g / m ² ) was used. The evaluation results are shown in Table 4.

(1) Cleanability After printing 3,000 images with a printing ratio of 5%, five halftone images with a toner loading of 0.20 mg / cm ² were printed and evaluated.
A: No defective cleaning image, no charging roller contamination.
B: No defective cleaning image and charging roller contamination.
C: A cleaning failure can be confirmed on the halftone image.

(2) Solid followability after standing After the above cleaning evaluation, it was left for 3 days in a low temperature and low humidity environment (15 ° C., 10% RH). After standing, ^two solid images having a toner loading of 0.45 mg / cm ² were printed, and the solid followability was evaluated. The image density was measured using “Macbeth reflection densitometer RD918” (manufactured by Macbeth).
A: The difference between the density at the leading edge of the first solid image and the density at the trailing edge of the second sheet is less than 0.10.
B: The density difference is 0.10 or more and less than 0.20.
C: The density difference is 0.20 or more.

(3) Cleaning property after being left After performing the solid followability evaluation, the toner is left again in a low temperature and low humidity environment (15 ° C., 10% RH) for 3 days, and the applied amount of toner is 0.20 mg / cm ² . Ten sheets of halftone images were printed and the cleaning property was evaluated.
A: No defective cleaning image.
B: A cleaning failure can be confirmed on the halftone image, but disappeared by the 10th sheet.
C: A cleaning failure can be confirmed on the halftone image, and it occurs even on the 10th sheet.

(4) Transferability after high-temperature storage After storing in the high-temperature and high-humidity storage environment, 10,000 images with a printing ratio of 2% were printed in a high-temperature and high-humidity environment (30 ° C./80% RH). Thereafter, a solid image with a toner loading of 0.45 mg / cm ² was output, and the transfer efficiency was determined from the change in weight between the toner amount on the photoreceptor and the toner amount on the evaluation paper (the toner amount on the photoreceptor was The transfer efficiency is 100% when the entire amount is transferred onto the evaluation paper).
A: Transfer efficiency is 95% or more.
B: Transfer efficiency is 90% or more and less than 95%.
C: Transfer efficiency is less than 90%.

(5) Solid followability after high-temperature storage After performing the above transferability evaluation, ^two solid images having a toner loading of 0.45 mg / cm ² were printed, and the solid followability was evaluated.
A: The difference between the density at the leading edge of the first solid image and the density at the trailing edge of the second sheet is less than 0.10.
B: The density difference is 0.10 or more and less than 0.20.
C: The density difference is 0.20 or more.

(6) Fog after high-temperature storage After performing the above-mentioned solid followability evaluation, it was left for 3 days in a high-temperature and high-humidity environment (30 ° C./80% RH). After leaving, an image having a white background portion is output, and the fog density ( %) And image fog was evaluated. An amberlite filter was used as the filter.
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more

[Examples 2 to 13, Comparative Examples 1 to 4]
Using the toner shown in Table 4, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 4.

  1: main body casing, 2: rotating body, 3, 3a, 3b: stirring member, 4: jacket, 5: raw material inlet, 6: product outlet, 7: central shaft, 8: drive unit, 9: processing space, 10: Rotating body end side surface, 11: Rotating direction, 12: Return direction, 13: Feeding direction, 16: Inner piece for raw material inlet, 17: Inner piece for product outlet, d: Overlapping portion of stirring member Interval, D: Width of stirring member

Claims (6)

In a toner having toner particles containing a binder resin and two or more inorganic fine particles,
(1) The toner contains 1.5 to 3.0 parts by mass of the inorganic fine particles as a total amount of two or more inorganic fine particles with respect to 100.0 parts by mass of the toner particles.
At least two kinds of the inorganic fine particles have a content of inorganic fine particles having a particle size of 30 nm or less of 80% by mass or more,
The inorganic fine particles contain inorganic fine particles A having a primary particle number average particle diameter of 7 nm, and the content of the inorganic fine particles A is 0.5 parts by mass or more with respect to 100.0 parts by mass of the toner particles. 1.8 parts by mass or less,
(2) The tap density of the toner, and a 0.62 g / cm ³ or more 0.68 g / cm ³ or less,
(3) A toner characterized in that Et100 of the toner is 200 mJ or more and 350 mJ or less.
[However, Et100 (mJ) is a powder fluidity analyzer that allows a powder to enter the toner powder layer in the container vertically while rotating the peripheral speed of the outermost edge of the propeller blade at 100 mm / sec. It represents the sum of the rotational torque and the vertical load obtained when measurement starts from a position 100 mm from the bottom of the layer and enters a position 10 mm from the bottom. ]   The toner according to claim 1, wherein the Et100 is 250 mJ or more and 350 mJ or less. The toner according to claim 1, wherein the tap density is 0.64 g / cm ³ or more and 0.66 g / cm ³ or less.   The toner according to claim 1, wherein the toner has an average circularity of 0.970 or more.   The toner according to claim 1, wherein the inorganic fine particles A are silica fine particles. The silica fine particles are a surface treated product with silicone oil,
In the silica fine particles, the amount of extracted silicone oil using hexane is 0.50% by mass or less,
The toner according to claim 5, wherein the silica fine particles have a hydrophobicity of 95% or more.

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