JP7071202B2 - toner - Google Patents

Description

The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method.

Copiers and printers are required to be smaller, faster, and have a longer life. In order to meet such demands, many toners manufactured by the emulsification aggregation method have been proposed in that the range of material selectivity is wide, the toner shape can be easily controlled, and a large amount of mold release agent can be contained. Has been done. Nowadays, copiers and printers have become widespread, and in addition to the above demands, it is required to obtain stable images in all environments.
In the toner produced by the emulsification aggregation method, the surfactant used at the time of production remains, so that "fog" in which the toner is scattered on the non-image area is likely to occur at high temperature and high humidity (for example, 30 ° C. and 80% RH). Therefore, various techniques are disclosed for improvement.
For example, a toner containing a surfactant containing a fluorine atom has been proposed for the purpose of improving the suppression of fog in a high temperature and high humidity environment (Patent Document 1). According to this, it is disclosed that the rising property of charging is improved by the surfactant containing a fluorine atom remaining in the toner.
Further, in Patent Document 2, in a toner containing toner particles and titanium oxide, the amount of residual surfactant contained in the toner particles, the content of divalent or trivalent metal elements, and the amount of water-soluble components of titanium oxide are adjusted. The toner is disclosed. According to this, it is disclosed that the influence on the charge due to the environmental change can be suppressed.

Japanese Unexamined Patent Publication No. 2014-178530 Japanese Unexamined Patent Publication No. 2002-287410

Certainly, the toners described in Patent Document 1 and Patent Document 2 have improved charge rise in a high temperature and high humidity environment, and a stable image can be obtained. However, as a result of diligent studies by the present inventors, any of the disclosed techniques has a new problem that regulation defects occur in an extremely low temperature environment (1 ° C.) when the speed is increased and the life is extended. I found out that.
An object of the present invention is to provide a toner having excellent durability and capable of maintaining high image quality regardless of the environment.

The present invention comprises toner particles having a binder resin and a surfactant , and
Titanate metal fine particles and
Toner with
The metal titanate fine particles are
(A) Number of primary particles The average particle size is 10 nm or more and 100 nm or less.
(B) In the methanol wettability test, when the transmittance of light having a wavelength of 780 nm is 50%, the methanol concentration is 30.0% or more and 68.0% or less .
The surface of the metal titanate fine particles is treated with any two or more of the surface treatment agents having a structure represented by the formula (1) or (2) described later.
It is a toner characterized by that.

In the toner produced by the emulsification aggregation method, it is possible to provide a toner that suppresses fog in a high temperature and high humidity environment, is excellent in poor regulation in an extremely low temperature environment, and can maintain high image quality through durability regardless of the environment.

Hereinafter, the present invention will be described in detail.

The present inventors have diligently studied to improve regulation defects in an extremely low temperature environment while maintaining fog suppression in a high temperature and high humidity environment in a toner having toner particles and a surfactant. as a result,
(A) Number of primary particles The average particle size is 10 nm or more and 100 nm or less.
(B) In the methanol wettability test, the above object is achieved by combining with fine metal titanate having a methanol concentration of 30.0% or more and 68.0% or less when the transmittance of light having a wavelength of 780 nm is 50%. I found out what I could do. The reason is not clear, but the present inventors think as follows.

First, considering the surface of the toner of the present invention briefly, the bottom layer is the toner particles, then the surfactant, and finally the metal titanate fine particles in this order. In addition, there is not a little water vapor (water) in the atmosphere. Since the toner of the present invention has a surfactant that is easily compatible with water, water in the atmosphere is more likely to be adsorbed by the surfactant on the surface of the toner particles than the toner without the surfactant. Therefore, on the surface of the toner particles of the present invention, the surface of the toner particles and the metal titanate fine particles are connected by water due to the water adsorbed on the surfactant. As a result, it is considered that the excessive charge on the surface of the toner particles generated during charging leaks to the metal titanate fine particles through water, and the charge of the toner becomes uniform. Therefore, the present inventors infer that the toner of the present invention is good at suppressing defective regulation even in an extremely low temperature environment.

It has been clarified by examination that the number average particle size of the primary particles of the metal titanate fine particles used in the toner of the present invention is indispensable to be 10 nm or more and 100 nm or less in order to exhibit such an action. The reason is that if the number average particle size of the primary particles of the metal titanate fine particles is smaller than 10 nm, the metal titanate fine particles are likely to be embedded in the toner due to the stress in the developer at the time of printing. As a result, it is difficult to fully exhibit the charge leakage characteristics of the metal titanate fine particles through durability. If it is larger than 100 nm, it is difficult to uniformly adhere the metal titanate fine particles to the surface of the toner particles, so that the effect of the metal titanate fine particles cannot be obtained.

Further, the metal titanate fine particles used in the present invention have a methanol concentration of 30.0% or more and 68.0% or less when the transmittance of light having a wavelength of 780 nm is 50% in a wettability test with a mixed solvent of methanol / water. Is essential. Hereinafter, the concentration of methanol when the transmittance of light having a wavelength of 780 nm is 50% in the wettability test with a mixed solvent of methanol / water is referred to as the degree of hydrophobicity.

When the degree of hydrophobicity is 30.0% or more, the fluctuation of water adsorption on the surface of the metal titanate fine particles due to the environment can be suppressed, and the change in developability for each environment can be suppressed. When the degree of hydrophobization is lower than 30.0%, the amount of charge is particularly reduced in a high temperature and high humidity environment. However, it was found that if the hydrophobicity becomes too high, the charge leakage property cannot be ensured in a low temperature and low humidity environment. It is presumed that this is probably because the metal titanate fine particles cannot adsorb water, so that the metal titanate fine particles and the surface layer of the toner particles cannot be connected via water. The wettability required to obtain the charge leakage effect due to water was 68.0% or less in terms of the degree of hydrophobicity. The degree of hydrophobicity of the metal titanate fine particles can be controlled by adjusting the surface treatment conditions of the metal titanate fine particles.

Hereinafter, the metal titanate fine particles, which are one of the constituent elements in the present invention, will be described.

The content of the metal titanate fine particles is preferably 0.4% by mass or more and 1.5% by mass or less based on the mass of the toner from the viewpoint of rising charge.

Further, it is preferable that the metal titanate fine particles are treated fine particles made of any compound having a structure represented by the general formula (1) or (2). Since the external additive containing fluorine has a structure having a high negative charge, the rising property of charging is high from the initial stage of durability, and the suppression of fog is further improved in a high temperature and high humidity environment.

（式（１）中、Ｒａ～Ｒｆは水素原子、炭素数１以上１０以下のアルキル基又は炭素数１以上１０以下のフッ化アルキル基を表す。Ｒａ～Ｒｆの少なくとも一つは炭素数１以上１０以下のフッ化アルキル基を表す。）

(In the formula (1), Ra to Rf represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms or an alkyl fluoride group having 1 or more and 10 or less carbon atoms. At least one of Ra to Rf has 1 or more carbon atoms. Represents an alkyl fluoride group of 10 or less.)

（式（２）中、Ｒｇは炭素数１以上１０以下のフッ化アルキル基を表し、Ｒｈは水素原子又は炭素数１以上３以下のアルコキシ基を表す。）

(In the formula (2), Rg represents an alkyl fluoride group having 1 or more and 10 or less carbon atoms, and Rh represents a hydrogen atom or an alkoxy group having 1 or more and 3 or less carbon atoms.)

Examples of the metal titanate fine particles include alkali metal titanate fine particles such as strontium titanate fine particles, calcium titanate fine particles, and magnesium titanate fine particles; and alkali metal titanate fine particles such as potassium titanate fine particles. Of these, strontium titanate fine particles are preferable.

The metal titanate fine particles may be surface-coated with a separate treatment agent in addition to the above-mentioned treatment agent in order to adjust the charge and improve the environmental stability.

As a treatment agent
Titanium coupling agent;
Silane coupling agent;
Silicone oil;
Fatty acid metal salts such as zinc stearate, sodium stearate, calcium stearate, zinc laurate, aluminum stearate, magnesium stearate;
Fatty acids such as stearic acid;
Can be exemplified.

Treatment methods include a wet method in which a surface treatment agent is dissolved / dispersed in a solvent, fine particles of titanate are added thereto, and the solvent is removed while stirring, a coupling agent, a fatty acid metal salt and titanium. Examples thereof include a dry method in which fine particles of the acid salt are directly mixed and treated while stirring.

The metal titanate fine particles can be produced, for example, by a normal pressure heating reaction method. At this time, it is preferable to use a mineral acid deflated product of a hydrolyzate of a titanium compound as a titanium oxide source and a water-soluble acidic metal compound as a metal source other than titanium. Then, it can be produced by a method of reacting the mixed solution of the raw materials while adding an alkaline aqueous solution at 60 ° C. or higher, and then treating with an acid. Further, as a method of controlling the shape of the metal titanate particles, there is also a method of performing a dry mechanical treatment.

Hereinafter, the normal pressure heating reaction method will be described.

As the titanium oxide source, a mineral acid defoliated product of a hydrolyzate of a titanium compound is used. Preferably, the pH of metatitanic acid obtained by the sulfuric acid method having an SO ₃ content of 1.0% by mass or less, more preferably 0.5% by mass or less is adjusted to 0.8 or more and 1.5% or less with hydrochloric acid. Use the one that has been deflated. On the other hand, as a metal source other than titanium, metal nitrate or hydrochloride can be used.

As the nitrate, for example, strontium nitrate, magnesium nitrate, calcium nitrate and the like can be used. As the hydrochloride salt, for example, strontium chloride, magnesium chloride, calcium chloride and the like can be used. When manufactured using nitrates or hydrochlorides of strontium, calcium, and magnesium, the obtained metal titanate particles have a perovskite crystal structure, which is preferable in that the environmental stability of charging is further improved.

As the alkaline aqueous solution, caustic alkali can be used, but the sodium hydroxide aqueous solution is particularly preferable.

Factors that affect the particle size of the obtained metal titanate particles in the production method include the pH when thawing metatitanium acid with hydrochloric acid, the mixing ratio of the titanium oxide source and the metal source other than titanium, and the initial stage of the reaction. Examples include the titanium oxide source concentration, the temperature at which the alkaline aqueous solution is added, the addition rate, the reaction time, and the stirring conditions.

These factors can be appropriately adjusted to obtain metal titanate particles having a desired particle size and particle size distribution. In addition, it is preferable to prevent the mixing of carbon dioxide gas by reacting in a nitrogen gas atmosphere in order to prevent the formation of carbon dioxide in the reaction process.

By increasing the concentration of the titanium oxide source at the initial stage of the reaction, the number average particle size of the primary particles of the metal titanate particles can be reduced.

When the temperature at which the alkaline aqueous solution is added is 100 ° C. or higher, a pressure vessel such as an autoclave is required, and a practical range of 60 ° C. or higher and 100 ° C. or lower is appropriate.

As for the addition rate of the alkaline aqueous solution, the slower the addition rate, the larger the particle size of the metal titanate particles can be obtained, and the faster the addition rate, the smaller the metal titanium acid particles having the particle size can be obtained.

In the production method, it is preferable to further acid-treat the metal titanate particles obtained by the atmospheric heating reaction. When the titanium acid metal particles are produced by performing a normal pressure heating reaction, if the mixing ratio of the titanium oxide source and the metal source other than titanium is MO / TiO ₂ (molar ratio) exceeds 1.40, the reaction is completed. The remaining unreacted metal source other than titanium reacts with carbon dioxide in the air to easily generate impurities such as metal carbonate. Further, if impurities such as metal carbonate remain on the surface, it becomes difficult to uniformly coat the surface treatment agent due to the influence of the impurities when performing the surface treatment for imparting hydrophobicity. Therefore, after adding the alkaline aqueous solution, it is advisable to carry out acid treatment in order to remove the unreacted metal source.

In the acid treatment, it is preferable to adjust the pH to 2.5 or more and 7.0 or less using hydrochloric acid, and more preferably to adjust the pH to 4.5 or more and 6.0 or less.

As the acid, nitric acid, acetic acid and the like can be used for the acid treatment in addition to hydrochloric acid. When sulfuric acid is used, metal sulfate having low solubility in water is likely to be generated.

Next, the toner particles, which are one of the constituent elements in the present invention, will be described.

[About surfactants]
It is essential that the toner of the present invention contains a surfactant. Although the reason is not clear, the present inventors adsorb water on the surface of the toner particles as described above, and further, the metal titanate fine particles that easily adsorb water are passed through water in the vicinity of the presence of the surfactant. I think this is to selectively attach them.

Examples of the surfactant that can be used in the toner of the present invention include sulfate ester-based, sulfonate-based, carboxylate-based, phosphate ester-based, and soap-based anionic surfactants. In addition, cationic surfactants such as amine salt type and quaternary ammonium salt type can be mentioned. Further, polyethylene glycol-based, aliphatic alcohols, nonionic surfactants in which alkylene oxide is added to fatty acids and the like can be mentioned.

Among these surfactants, anionic surfactants are preferable from the viewpoint of negative chargeability of the toner, and more preferably anionic surfactants containing a phosphorus element or a sulfur element are preferable.

As a method of adding the surfactant, there are a method of adding the toner particles at the time of producing the toner particles, a method of adding the surfactant at the time of the external addition step, and the like. Among them, the toner of the present invention is produced by using an emulsion aggregation method which is used at the time of producing toner particles and whose amount of surfactant present on the surface can be easily adjusted in the process.

The amount of the surfactant on the surface of the toner particles of the present invention is preferably 10 ppm or more and 300 ppm or less from the viewpoint of the saturated charge amount and the charge rise in a high temperature and high humidity environment.

Further, the toner of the present invention measures the atomic strength (TRA) derived from the surfactant (S or P) measured using the toner particles as a measurement sample and the toner by using X-ray photoelectron spectroscopy (ESCA). A ratio of TRB / TRA to the atomic strength (TRB) of the metal titanate fine particles (Ti) measured as a sample is 0.5 or more, which is good for suppressing fog in a high temperature and high humidity environment and in an extremely low temperature environment. It is preferable from the viewpoint that the poor regulation in the above can be further improved.

[About binding resin]
As the binder resin, a vinyl resin, a polyester resin and the like can be preferably exemplified. Examples of the vinyl resin, polyester resin and other binder resin include the following resins or polymers.

Monopolymers of styrene and its substituents such as polystyrene, polyvinyltoluene; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene -Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer Stylized copolymers such as coalesced, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethylmethacrylate, polybutylmethacrylate, poly Vinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. These binder resins can be used alone or in combination.

[Crosslinking agent]
In order to control the molecular weight of the binder resin constituting the toner particles, a cross-linking agent may be added during the polymerization of the polymerizable monomer.

For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, 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 Examples thereof include diacrylate (MANDA Nihonkayaku) and those obtained by converting the above acrylate into methacrylate.

The amount of the cross-linking agent added is preferably 0.001% by mass or more and 15,000% by mass or less with respect to the polymerizable monomer.

[About mold release agent]
In the present invention, it is preferable to contain a mold release agent as one of the materials constituting the toner particles. Examples of the release agent that can be used for the toner particles include paraffin wax, microcrystallin wax, petroleum wax such as petrolatum and its derivatives, Montan wax and its derivatives, hydrocarbon wax and its derivatives by the Fisher Tropsch method, polyethylene, and the like. Polyolefin waxes and derivatives thereof such as polypropylene, natural waxes and derivatives thereof such as carnauba wax and candelilla wax, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes and ester waxes. , Ketone, hardened castor oil and its derivatives, vegetable waxes, animal waxes, silicone resins and the like. Derivatives include oxides, block copolymers with vinyl-based monomers, and graft-modified products. The content of the release agent is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer.

[About colorants]
In the present invention, the case where the toner particles contain a colorant is not particularly limited, and the known ones shown below can be used.

Examples of the yellow pigment include condensed azo compounds such as yellow iron oxide, nables yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartradin lake. Isoindolinone compounds, anthraquinone compounds, azometal complexes, methine compounds, and allylamide compounds are used. Specifically, the following can be mentioned.

C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

Condensations of magenta pigments such as Bengala, Permanent Red 4R, Resole Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Laked D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamin Lake B, Alizarin Lake, etc. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthracinone, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, the following can be mentioned.

C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254.

Cyan pigments include copper phthalocyanine compounds such as alkaline blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, and induslen blue BG and their derivatives, anthracinone compounds, and basic dyes. Examples include lake compounds. Specifically, the following can be mentioned.

C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

Examples of the white pigment include zinc oxide, titanium oxide, antimony white, and zinc sulfide.

Examples of the black pigment include those colored black using carbon black, aniline black, non-magnetic ferrite, magnetite, the above-mentioned yellow colorant, magenta colorant and cyan colorant. These colorants can be used alone or in admixture, and even in the form of a solid solution.

The content of the colorant is preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer.

[About charge control agent]
In the present invention, the toner particles may contain a charge control agent. As the charge control agent, known ones can be used. Examples of the charge control agent for controlling the toner particles in a load electric manner include the following.

Examples of the organic metal compound and the chelate compound include a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an oxycarboxylic acid and a dicarboxylic acid-based metal compound. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides or esters, phenol derivatives such as bisphenols and the like. Further, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calix arelanes can be mentioned.

These charge control agents can be contained alone or in combination of two or more. Further, when a charge control agent containing a metal is used in the toner of the present invention, care must be taken so that the resistivity and content of the metal do not deviate from the range of the present invention. The amount of these charge control agents added is preferably 0.01 parts by mass or more and 10.00 parts by mass or less with respect to 100.00 parts by mass of the binder resin.

[Manufacturing method of toner particles]
As the method for producing toner particles of the present invention, a known means can be used, and a kneading and pulverizing method or a wet production method can be used. From the viewpoint of uniform particle size and shape controllability, a wet manufacturing method can be preferably used. Further, examples of the wet production method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method, and the emulsion aggregation method can be preferably used in the present invention. This is because a surfactant is used to disperse the binder resin in the aqueous medium, and the cleaning step is performed after the toner particles are formed, so that the amount of the surfactant on the surface of the toner particles can be easily adjusted. be.

In the emulsification aggregation method, first, materials such as fine particles of the binder resin and a colorant are dispersed and mixed with a dispersion stabilizer. Then, by adding a flocculant, the toner is aggregated until the desired toner particle size is reached, and then or at the same time as the aggregation, fusion between the resin fine particles is performed. Further, it is a method of forming toner particles by controlling the shape by heat as needed. Here, the fine particles of the binder resin may be composite particles formed of a plurality of layers having two or more layers made of resins having different compositions. For example, it can be produced by an emulsification polymerization method, a miniemulsion polymerization method, a phase inversion emulsification method, or the like, or can be produced by combining several production methods.

When the toner particles contain an internal additive, the resin fine particles may contain the internal additive, or a dispersion of the internal additive fine particles consisting of only the internal additive is separately prepared and added. When the agent fine particles are aggregated with the resin fine particles, they may be aggregated together. Further, it is also possible to produce toner particles having a layer structure having different compositions by adding resin fine particles having different compositions at the time of aggregation and aggregating them at different times.

The following can be used as the dispersion stabilizer.

As the surfactant, known cationic surfactants, anionic surfactants, and nonionic surfactants can be used.

As an inorganic dispersion stabilizer, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. , Bentonite, silica, alumina and the like.

Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, and starch.

Among these dispersion stabilizers, a surfactant is preferable in the present invention, and an anionic surfactant is more preferable from the viewpoint of charging.

[About external additives]
The toner of the present invention may contain an external additive other than the titanium acid metal fine particles. In particular, in order to improve the fluidity and chargeability of the toner, a fluidity improver may be added.

The following can be used as the fluidity improver. Examples thereof include fine powdered silica such as wet-processed silica and dry-processed silica, and treated silica whose surface is treated with a silane compound or silicone oil.

When the number average particle size of the primary particles is 5 nm or more and 30 nm or less, the fluidity improver is preferable because it can have high chargeability and fluidity.

Further, as the fluidity improver, treated silica fine powder obtained by hydrophobizing silica fine powder with silicone oil or / and a silane coupling agent is more preferable.

The fluidity improver preferably has a specific surface area of 30 m ² / g or more and 300 m ² / g or less due to nitrogen adsorption measured by the BET method.

It is preferable to use 0.01 parts by mass or more and 3 parts by mass or less of the fluidity improver in total with respect to 100 parts by mass of the toner particles.

Examples of the mixer externally attached to the toner particles include FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), super mixer (manufactured by Kawata Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), and hybridizer (manufactured by Nara Machinery Co., Ltd.). In addition, examples of the sieving device used for sieving the coarse particles after external addition include the following. Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheave, Gyroshifter (manufactured by Tokuju Kosakusho); Vibrasonic System (manufactured by Dalton); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo Cleaner (manufactured by Freund Turbo Industries) ); Micro shifter (manufactured by Makino Sangyo Co., Ltd.).

[Toner particle size]
The weight average particle size (D4) of the toner of the present invention is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 4.0 μm or more and 9.0 μm or less. This is advantageous in terms of durability and heat resistance in long-term use because the specific surface area of the toner is not large when the weight average particle size is 4.0 μm or more, and the toner has a weight average particle size of 9.0 μm or less. It is advantageous in terms of coloring power and image resolution. The weight average particle size of the toner of the present invention can be adjusted by the production conditions and classification at the time of toner production.

[About the average circularity of toner]
The average circularity of the toner of the present invention is preferably 0.960 or more. When it is 0.960 or more, the fine line reproducibility is also improved. More preferably, it is 0.970 or more.

The method for measuring various physical properties of the toner of the present invention will be described below.

<Number average particle size of primary particles of metal titanate fine particles>
The number average particle size of the primary particles of the metal titanate fine particles is measured using a transmission electron microscope "JEM-2800" (JEOL Ltd.). By observing the toner to which the metal titanate fine particles are externally attached, the major axis of 100 primary particles of the metal titanate fine particles is randomly measured in a field magnified up to 200,000 times to obtain the number average particle size. The observation magnification is appropriately adjusted according to the size of the metal titanate fine particles.

Confirmation that the external additive is metal titanate fine particles is carried out by STEM-EDS measurement.

The measurement conditions are as follows.
JEM2800 type transmission electron microscope: Acceleration voltage 200kV
EDS detector: JED-2300T (JEOL, element area 100mm ² ) is used. EDS analyzer: Noran System7 (Thermo Fisher Scientific) is used.
X-ray storage rate: 10,000 to 15,000 cps
Dead time: Adjust the electron dose to 20 to 30%, and perform EDS analysis (total number of times 100 times or measurement time 5 minutes).

<Mole ratio of M / Ti of metal fine particles of titanium acid>
The M and Ti contents of the metal titanate fine particles used in the present invention can be measured by a fluorescent X-ray analyzer. For example, using a wavelength-dispersed X-ray fluorescence analyzer Axios advanced (manufactured by PANalytical), 1 g of a sample is weighed on a cup dedicated to powder measurement recommended by PANalytical with a special film attached, and the sample is weighed under an atmospheric pressure He atmosphere. In, the elements from Na to U in the metal titanate fine particles are measured by the FP method. At that time, assuming that all the detected elements are oxides, the total mass of them is 100%, and the content of MO and TiO ₂ with respect to the total mass by software SpectraEvolution (version 5.0L) (mass%). ) Is calculated as an oxide conversion value. After that, M / Ti (mass ratio) obtained by removing oxygen from the quantification result is obtained, and then converted into M / Ti (molar ratio) from the atomic weight of each element.

<Degree of hydrophobicity of metal titanate fine particles>
The degree of hydrophobicity of the metal titanate fine particles was measured by a powder wettability tester "WET-100P" (manufactured by Reska).

A fluororesin-coated spindle-shaped rotor with a length of 25 mm and a maximum body diameter of 8 mm was placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm. After putting 70 ml of a hydrous methanol solution consisting of 50% by volume of methanol and 50% by volume of water in the cylindrical glass container, 0.5 g of metal titanate fine particles were added and set in a powder wettability tester. Methanol was added to the liquid at a rate of 0.8 mL / min through the above powder wettability tester while stirring at a rotation speed of 3.3 times / sec using a magnetic stirrer. The transmittance was measured with light having a wavelength of 780 nm, and the value represented by the volume percentage of methanol when the transmittance reached 50% (= (volume of methanol / volume of mixture) × 100) was defined as the degree of hydrophobicity. .. The volume ratio of initial methanol to water is adjusted as appropriate according to the degree of hydrophobization of the sample.

<Measuring method of weight average particle size (D4) of toner particles>
The weight average particle size (D4) of the toner particles is calculated as follows. As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electric resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels. As the electrolytic aqueous solution used for the measurement, one in which special grade sodium chloride is dissolved in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing the measurement and analysis, the dedicated software was set as follows. On the "Change standard measurement method (SOM)" screen of the dedicated software, set the total count number of the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check "Flash of aperture tube after measurement". On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put about 200 ml of the electrolytic aqueous solution in a 250 ml round bottom beaker made of glass dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Put about 30 ml of the electrolytic aqueous solution in a 100 ml flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a pH 7 precision measuring instrument consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.3 ml of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. About 3.3 liters of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of contaminantinone N is added into this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. For ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, drop the aqueous electrolyte solution of (5) in which toner is dispersed into the round-bottomed beaker of (1) installed in the sample stand, and adjust the measured concentration to about 5%. .. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner particles>
The average circularity of the toner was measured by a flow type particle image analyzer "FPIA-3000 type" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.

The measurement principle of the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to capture a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent into the flat sheath flow is sandwiched between the sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Moreover, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image has 512 pixels × 512 pixels in one field, and is image-processed at an image processing resolution of 0.37 × 0.37 μm per pixel, and the contour of each particle image is processed. Extraction is performed, and the projected area and peripheral length of the particle image are measured.

Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the diameter equivalent to a circle and the circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is the value obtained by dividing the peripheral length of the circle obtained from the circular equivalent diameter by the peripheral length of the particle projected image. It is defined and calculated by the following formula.
Circularity C = 2 × (π × S) ^1/2 / L

When the particle image is a perfect circle, the circularity becomes 1.000, and the greater the degree of unevenness on the outer circumference of the particle image, the smaller the circularity.

After calculating the circularity of each particle, the range of circularity 0.2 to 1.0 is divided into 800 channels, and the average value is calculated using the center value of each channel as a representative value to calculate the average circularity.

As a specific measurement method, 0.02 g of a surfactant, preferably sodium dodecylbenzene sulfonate, as a dispersant is added to 20 ml of ion-exchanged water, 0.02 g of a measurement sample is added, an oscillation frequency of 50 kHz, and electrical. A tabletop ultrasonic washer disperser with an output of 150 W (for example, "VS-150" (manufactured by Vervocrea, etc.) was used for dispersion treatment for 2 minutes to prepare a dispersion liquid for measurement. It is appropriately cooled so that the temperature of the above temperature is 10 ° C. or higher and 40 ° C. or lower.

The flow-type particle image analyzer equipped with a standard objective lens (10x) was used for the measurement, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is set to 85%. The diameter of the analyzed particle was limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less, and the average circularity of the toner was determined.

In the measurement, automatic focus adjustment is performed using standard latex particles (for example, 5200A manufactured by Duke Scientific is diluted with ion-exchanged water) before the start of the measurement. After that, it is preferable to perform focus adjustment every two hours from the start of measurement.

In the embodiment of the present application, a flow type particle image analyzer issued by Sysmex Corporation is used, and the diameter of the analysis particle is limited to 2.00 μm or more and 200.00 μm or less in equivalent circle diameter. Measured under the measurement and analysis conditions when the calibration certificate was received.

<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of the toner particles and various resins is measured by the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA-Instruments). Weigh 3 mg of the sample to be measured. This is placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed in a measurement temperature range of 20 to 200 ° C. at a heating rate of 1 ° C./min and at normal temperature and humidity. At this time, the modulation amplitude is ± 0.5 ° C. and the frequency is 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained rebirthing heat flow curve. Tg is obtained by determining the center value of the intersection of the baseline before and after endothermic process and the tangent line of the curve due to endothermic process as Tg (° C.).

<Surface abundance ratio TRA of the surfactant of the toner particles and the surface abundance ratio TRB of the metal titanate fine particles of the toner>
Elemental analysis of toner particles and the surface of the toner is performed using the following device under the following conditions.
-Measuring device: Quantum2000 (trade name, manufactured by ULVACFY Co., Ltd.)
・ X-ray source: Monochrome Al Kα
-Xray Setting: 100 μmφ (25W (15KV))
・ Photoelectron extraction angle: 45 degrees ・ Neutralization condition: Combined use of neutralization gun and ion gun ・ Analysis area: 300 × 200 μm
-Pass Energy: 58.70eV
-Step size: 0.125 eV
・ Analysis software: Maltipak (PHI)

The surface atomic concentration (atomic%) was calculated from the measured peak intensities of each element.

In the case of toner particles, the value obtained by dividing the number of atoms derived from the surfactant (element S or element P) by all the identified atoms was taken as the TRA.

Further, in the toner, the value obtained by dividing the number of atoms of Ti derived from the metal fine particles of titanium acid by all the identified atoms was taken as the TRB.

<Measurement of surface surfactant amount>
First, 50 ml of methanol and 10 g of toner are precisely weighed in a sample bottle and mixed well. Then, ultrasonic waves are irradiated for 30 minutes with a desktop ultrasonic cleaner (trade name "B2510J-MTH", manufactured by Branson) having an oscillation frequency of 42 kHz and an electrical output of 125 W. Then, filtration is performed using a solvent-resistant membrane filter "Maeshori Disc" having a pore diameter of 0.2 μm, manufactured by Tosoh Corporation. Methanol is removed from the filtrate by an evaporator, then dissolved in 10 mg of deuterated chloroform (1% TMS) containing trimethylsilane (TMS), and analyzed by 1H-NMR.

The amount of the surfactant extracted from the surface of the toner is calculated using a calibration curve based on the TMS strength, which is obtained by using the same surfactant as the surfactant contained in the toner in advance. The calibration curve is prepared from the TMS intensity and the peak intensity ratio derived from the surfactant.

The measuring device and measuring conditions are as follows.
Equipment: FT NMR equipment JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integrations: 1024 times Measurement temperature: 40 ° C

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto. Examples 12 to 19 are reference examples. In addition, the number of copies in the following formulation indicates a mass part.

<Production example of metal titanium acid fine particles 1>
After deironing and bleaching the metatitanic acid obtained by the sulfuric acid method, an aqueous sodium hydroxide solution was added to adjust the pH to 9.0, desulfurization was performed, and then neutralization to pH 5.8 with hydrochloric acid and washing with filtered water were performed. Water was added to the washed cake to make a slurry of 1.85 mol / L as TiO ₂ , and then hydrochloric acid was added to adjust the pH to 1.0 and degluing treatment was performed.

1.88 mol of desulfurized and deglutinized metatitanium acid was collected as TiO ₂ and placed in a 3 L reaction vessel. After 2.16 mol of an aqueous solution of strontium chloride was added to the deflated metatitanium acid slurry so as to have a SrO / TiO ₂ mol ratio of 1.15, the TiO ₂ concentration was adjusted to 1.023 mol / L. Next, after heating to 90 ° C. with stirring and mixing, 440 mL of a 10 N mol / L sodium hydroxide aqueous solution was added over 45 minutes, and then stirring was continued at 95 ° C. for 1 hour to complete the reaction.

The reaction slurry was cooled to 50 ° C., hydrochloric acid was added until the pH reached 5.0, and stirring was continued for 20 minutes. The obtained precipitate was decanted and washed, filtered and separated, and then dried in the air at 120 ° C. for 8 hours.

Subsequently, 300 g of the dried product was put into a dry particle composite device (Nobilta NOB-130 manufactured by Hosokawa Micron). The treatment was carried out at a treatment temperature of 30 ° C. and a rotary treatment blade of 90 m / sec for 10 minutes.

Further, hydrochloric acid was added to the dried product until the pH reached 0.1, and stirring was continued for 1 hour. The resulting precipitate was decanted and washed.

The slurry containing the precipitate was adjusted to 40 ° C., and hydrochloric acid was added to adjust the pH to 2.5. Next, 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane were added by stirring and mixing for 1 hour with respect to the solid content, and the stirring and holding was continued for 10 hours. After adding a 5N sodium hydroxide solution to adjust the pH to 6.5 and continuing stirring for 1 hour, the cake obtained by filtration and washing was dried in the air at 120 ° C. for 8 hours. The obtained metal titanate fine particles are referred to as metal titanate fine particles 1. Table 1 shows the physical properties of the obtained metal titanate fine particles 1. The isobutyltrimethoxysilane is the treatment agent 1, and the trifluoropropyltrimethoxysilane is the treatment agent 2.

<Production example of metal titanium acid fine particles 2>
3. With respect to Production Example 1 of strontium titanate particles, 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane to 4.0% by mass of isobutyltrimethoxysilane. The same operation was carried out except for making 2% by mass of octylsilane, to obtain metal titanate fine particles 2.

<Production example of metal titanium acid fine particles 3>
4. From 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane to 4.0% by mass of isobutyltrimethoxysilane and 4. with respect to Production Example 1 of strontium titanate particles. The same operation was carried out except that hexamethyldisilazane was produced in an amount of 0% by mass to obtain metal titanate fine particles 3.

<Production example of metal titanium acid fine particles 4>
Except for making 7.8% by mass of isobutyltrimethoxysilane from 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane with respect to Production Example 1 of strontium titanate particles. Performed the same operation to obtain metal titanate fine particles 4.

<Production example of metal titanium acid fine particles 5>
For Production Example 1 of strontium titanate particles, the TiO ₂ concentration to be adjusted after adding 2.16 mol of strontium chloride aqueous solution to 1.15 mol of SrO / TiO ₂ mol ratio to the deflated metatitanic acid slurry is adjusted. 1.104 mol / L, 4.0% by weight isobutyl from 4.6% by weight isobutyltrimethoxysilane and 4.6% by weight trifluoropropyltrimethoxysilane when added to solids The same operation was carried out except for making trimethoxysilane, to obtain metal titanate fine particles 5.

<Production example of metal titanium acid fine particles 6>
The same operation was performed with respect to Production Example 5 of Strontium Titanium Particles except that 4.0% by mass of isobutyltrimethoxysilane was changed to 15.0% by mass of isobutyltrimethoxysila, and the metal titanate fine particles 6 were obtained. Obtained.

<Production example of metal titanium acid fine particles 7>
With respect to Production Example 1 of strontium titanate particles, 2.54 mol of an aqueous solution of strontium chloride was added to the deflated metatitanic acid slurry so that the SrO / TiO ₂ mol ratio was 0.965 mol / 10 mol /. Add 440 mL of L sodium hydroxide solution over "45 minutes" and add over "60 minutes", 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass when added to the solid content. The same operation was carried out except that 3.5% by mass of trifluoropropyltrimethoxysilane was converted to 3.5% by mass of isobutyltrimethoxysilane to obtain metal titanate fine particles 7.

<Production example of metal titanium acid fine particles 8>
The same operation was performed with respect to Production Example 7 of Strontium Titanium Particles except that 3.5% by mass of isobutyltrimethoxysilane was changed to 12.0% by mass of isobutyltrimethoxysilane, and the metal titanate fine particles 8 were obtained. Obtained.

<Production example of metal titanium acid fine particles 9>
Except for making 15.0% by mass of isobutyltrimethoxysilane from 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane with respect to Production Example 1 of strontium titanate particles. Performed the same operation to obtain metal titanate fine particles 9.

<Production example of metal titanium acid fine particles 10>
With respect to Production Example 1 of strontium titanate particles, 2.54 mol of an aqueous solution of strontium chloride was added to the deflated metatitanic acid slurry so that the SrO / TiO ₂ mol ratio was 0.895 mol / 10 mol /. Add 440 mL of L sodium hydroxide solution over "45 minutes" and add over "70 minutes", 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass when added to the solid content. The same operation was carried out except that 3.4% by mass of trifluoropropyltrimethoxysilane was converted to 3.4% by mass of isobutyltrimethoxysilane, to obtain metal titanate fine particles 10.

<Production example of metal titanium acid fine particles 11>
Except for making 3.0% by mass of isobutyltrimethoxysilane from 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane with respect to Production Example 1 of strontium titanate particles. Performed the same operation to obtain metal titanate fine particles 11.

<Production example of metal titanium acid fine particles 12>
For Production Example 1 of strontium titanate particles, the TiO ₂ concentration to be adjusted after adding 2.16 mol of an aqueous solution of strontium chloride to a deflated metatitanic acid slurry so as to have a SrO / TiO ₂ mol ratio of 1.15 is adjusted. 1.121 mol / L, 2.0% by weight isobutyl from 4.6% by weight isobutyltrimethoxysilane and 4.6% by weight trifluoropropyltrimethoxysilane when added to solids The same operation was carried out except for making trimethoxysilane, to obtain metal titanate fine particles 12.

<Production Example of Metal Titanate Fine Particles 13>
Hydrolyzed titanium hydroxide obtained by adding aqueous ammonia to the titanium tetrachloride aqueous solution was washed with pure water, and 0.25% sulfuric acid was added as SO ₃ to the titanium hydroxide slurry to the titanium hydroxide slurry. bottom.

Next, hydrochloric acid was added to the hydroxide-containing titanium slurry to adjust the pH to 0.65 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 4.7, and washing was repeated until the electrical conductivity of the supernatant reached 50 μS / cm.

A 0.95 times molar amount of strontium hydroxide octahydrate was added to the titanium hydroxide-containing titanium, and the mixture was placed in a SUS stainless steel reaction vessel and replaced with nitrogen gas. Further, distilled water was added so as to be 0.6 mol mol / L in terms of SrTiO ₃ .

The slurry was heated to 65 ° C. at 10 ° C./hour in a nitrogen atmosphere, and the reaction was carried out for 8 hours after reaching 65 ° C. After the reaction, the mixture was cooled to room temperature, the supernatant was removed, and then washing with pure water was repeated.

Further, under a nitrogen atmosphere, the above slurry was placed in an aqueous solution in which 2% by mass of sodium stearate was dissolved with respect to the solid content of the slurry, and a magnesium sulfate aqueous solution was added dropwise with stirring to add stearic acid to the surface of the perovskite-type crystal. Magnesium was precipitated.

The slurry was repeatedly washed with pure water and then filtered through Nutche, and the obtained cake was dried to obtain metal titanate fine particles 13 surface-treated with magnesium stearate.

<Production example of metal titanium acid fine particles 14>
4. With respect to Production Example 1 of strontium titanate particles, 4.6% by mass of isobutyltrimethoxysilane and 4.6% by mass of trifluoropropyltrimethoxysilane to 4.6% by mass of isobutyltrimethoxysilane. The same operation was performed except that 6% by mass of 1,3-bis (3,3,3-trifluoropropyl) -1,1,3,3-tetramethylpropanedisilazane was used to remove the metal titanate fine particles 14. Obtained.

Table 1 shows the physical properties of the metal titanate fine particles 2 to 14.

<Preparation of binder resin particle dispersion liquid 1>
78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution of 150 parts of ion-exchanged water of 0.5 part of Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to this solution and dispersed. Further, while stirring slowly for 10 minutes, an aqueous solution of 0.3 parts of potassium persulfate and 10 parts of ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature and ion-exchanged water was added to obtain a resin particle dispersion 1 having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

<Preparation of binder resin particle dispersion liquid 2>
78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution of 150 parts of ion-exchanged water of 0.5 part of Huosphanol ML-200 (manufactured by Toho Chemical Industry Co., Ltd.) was added to this solution and dispersed. Further, while stirring slowly for 10 minutes, an aqueous solution of 0.3 parts of potassium persulfate and 10 parts of ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a resin particle dispersion liquid 2 having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

<Preparation of binder resin particle dispersion liquid 3>
78.0 parts of styrene, 20.7 parts of butyl acrylate, 1.3 parts of acrylic acid as a carboxyl group-imparting monomer, and 3.2 parts of n-lauryl mercaptan were mixed and dissolved. An aqueous solution of 0.5 part of Epan 450 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 150 parts of ion-exchanged water was added to this solution and dispersed. Further, while stirring slowly for 10 minutes, an aqueous solution of 0.3 parts of potassium persulfate and 10 parts of ion-exchanged water was added. After nitrogen substitution, emulsion polymerization was carried out at 70 ° C. for 6 hours. After completion of the polymerization, the reaction solution was cooled to room temperature, and ion-exchanged water was added to obtain a resin particle dispersion liquid 3 having a solid content concentration of 12.5% by mass and a volume-based median diameter of 0.2 μm.

<Preparation of mold release agent dispersion 1>
Mix 100 parts of mold release agent (behenic behenate, melting point: 72.1 ° C.) and 0.5 part of Neogen RK with 385 parts of ion-exchanged water, and use a wet jet mill JN100 (manufactured by Joko Co., Ltd.) for about 1 hour. The mixture was dispersed to obtain a release agent dispersion liquid 1. The concentration of the release agent dispersion liquid 1 was 20% by mass.

<Preparation of mold release agent dispersion 2>
About 100 parts of a mold release agent (behenic behenate, melting point: 72.1 ° C.) and 0.5 part of Huosphanol ML-200. The mixture was dispersed for 1 hour to obtain a release agent dispersion liquid 2. The concentration of the release agent dispersion liquid 2 was 20% by mass.

<Preparation of mold release agent dispersion 3>
Mix 100 parts of a mold release agent (behenic behenate, melting point: 72.1 ° C.) and 0.5 part of Epan 450 with 385 parts of ion-exchanged water, and use a wet jet mill JN100 (manufactured by Joko Co., Ltd.) for about 1 part. The release agent dispersion 3 was obtained by dispersion over time. The concentration of the release agent dispersion liquid 3 was 20% by mass.

<Preparation of colorant dispersion 1>
As a colorant, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 0.5 part of Neogen RK are mixed with 885 parts of ion-exchanged water and dispersed for about 1 hour using a wet jet mill JN100. Dispersion liquid 1 was obtained.

<Preparation of colorant dispersion 2>
As a colorant, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 0.5 part of Huosphanol ML-200. 5 parts are mixed with 885 parts of ion-exchanged water and dispersed for about 1 hour using a wet jet mill JN100. Colorant dispersion 2 was obtained.

<Preparation of colorant dispersion 3>
As a colorant, 100 parts of carbon black "Nipex35 (manufactured by Orion Engineered Carbons)" and 0.5 part of Epan 450 are mixed with 885 parts of ion-exchanged water and dispersed for about 1 hour using a wet jet mill JN100 for coloring. Agent dispersion 3 was obtained.

<Manufacturing example of toner particles 1>
1265 parts of the resin particle dispersion liquid, 10 parts of the release agent dispersion liquid, and 10 parts of the colorant dispersion liquid were dispersed using a homogenizer (manufactured by IKA: Ultratarax T50). The temperature inside the container was adjusted to 30 ° C. with stirring, and 1N aqueous sodium hydroxide solution was added to adjust the pH to 8.0 (pH adjustment 1). As a flocculant, an aqueous solution prepared by dissolving 0.25 parts of aluminum chloride in 10 parts of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After leaving it for 3 minutes, the temperature was started to be raised to 50 ° C. to generate associated particles. In that state, the particle size of the associated particles is measured with "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). When the weight average particle size reached 6.3 μm, 0.9 part of sodium chloride and 0.5 part of Neogen RK were added to stop the particle growth.

After adjusting the pH to 9.0 by adding 1N aqueous sodium hydroxide solution, the temperature was raised to 95 ° C. to make the aggregated particles spherical. When the average circularity reached 0.980, the temperature was lowered, and the mixture was cooled to room temperature to obtain the toner particle dispersion liquid 1.

Hydrochloric acid was added to the obtained toner particle dispersion 1 to adjust the pH to 1.5 or less, and the mixture was left to stir for 1 hour and then solid-liquid separated by a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 5.0 μS / cm or less, and then the solid-liquid separation was finally performed to obtain a toner cake. The obtained toner cake was dried and further classified using a classifier so that the weight average particle size was 6.3 μm to obtain toner particles 1.

<Manufacturing example of toner particles 2>
The toner particles 2 were obtained in the same manner except that 0.5 part of neogen RK added when the particle growth of the toner particles 1 was stopped was changed to 0.1 part of neogen RK.

<Manufacturing example of toner particles 3>
Toner particles 3 were obtained in the same manner except that 0.5 part of Neogen RK added when the particle growth of the toner particles 1 was stopped was changed to 2.5 parts of Neogen RK.

<Manufacturing example of toner particles 4>
265 parts of the resin particle dispersion liquid, 2 10 parts of the release agent dispersion liquid, and 10 parts of the colorant dispersion liquid 2 were dispersed using a homogenizer (manufactured by IKA: Ultratarax T50). The temperature inside the container was adjusted to 30 ° C. with stirring, and 1N aqueous sodium hydroxide solution was added to adjust the pH to 8.0 (pH adjustment 1). As a flocculant, an aqueous solution prepared by dissolving 0.25 parts of aluminum chloride in 10 parts of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After leaving it for 3 minutes, the temperature was started to be raised to 50 ° C. to generate associated particles. In that state, the particle size of the associated particles is measured with "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). When the weight average particle size reached 6.3 μm, 0.9 part of sodium chloride and 2.5 parts of Huosphanol ML-200 were added to stop the particle growth.

After adjusting the pH to 9.0 by adding 1N aqueous sodium hydroxide solution, the temperature was raised to 95 ° C. to make the aggregated particles spherical. When the average circularity reached 0.980, the temperature was lowered, and the mixture was cooled to room temperature to obtain a toner particle dispersion liquid 4.

Hydrochloric acid was added to the obtained toner particle dispersion 4 to adjust the pH to 1.5 or less, and the mixture was left to stir for 1 hour and then solid-liquid separated by a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 5.0 μS / cm or less, and then the solid-liquid separation was finally performed to obtain a toner cake. The obtained toner cake was dried and further classified using a classifier so that the weight average particle size was 6.3 μm to obtain toner particles 4.

<Manufacturing example of toner particles 5>
265 parts of the resin particle dispersion liquid 3, 10 parts of the release agent dispersion liquid, and 10 parts of the colorant dispersion liquid 3 were dispersed using a homogenizer (manufactured by IKA: Ultratarax T50). The temperature inside the container was adjusted to 30 ° C. with stirring, and 1N aqueous sodium hydroxide solution was added to adjust the pH to 8.0 (pH adjustment 1). As a flocculant, an aqueous solution prepared by dissolving 0.25 parts of aluminum chloride in 10 parts of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After leaving it for 3 minutes, the temperature was started to be raised to 50 ° C. to generate associated particles. In that state, the particle size of the associated particles is measured with "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter). When the weight average particle size reached 6.3 μm, 0.9 part of sodium chloride and 2.5 parts of Epan 450 were added to stop the particle growth.

After adjusting the pH to 9.0 by adding 1N aqueous sodium hydroxide solution, the temperature was raised to 95 ° C. to make the aggregated particles spherical. When the average circularity reached 0.980, the temperature was lowered, and the mixture was cooled to room temperature to obtain a toner particle dispersion liquid 5.

Hydrochloric acid was added to the obtained toner particle dispersion 5 to adjust the pH to 1.5 or less, and the mixture was left to stir for 1 hour and then solid-liquid separated by a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion liquid again, and then solid-liquid separation was performed with the above-mentioned filter. The reslurry and solid-liquid separation were repeated until the electric conductivity of the filtrate became 5.0 μS / cm or less, and then the solid-liquid separation was finally performed to obtain a toner cake. The obtained toner cake was dried and further classified using a classifier so that the weight average particle size was 6.3 μm to obtain toner particles 5.

Table 2 shows the physical properties of the toner particles 1 to the toner particles 5.

<Manufacturing example of toner 1>
For the toner particles 1 (100 parts) obtained above, 0.8 parts of metal titanium acid fine particles and 1.0 part of RX300 (manufactured by Aerosil Japan) were used at 3600 rpm with a Henshell mixer FM10C (manufactured by Mitsui Mining Co., Ltd.). Dry mixing was performed for 12 minutes under the conditions to obtain toner 1. Table 3 shows the physical characteristics of the obtained toner.

<Toner manufacturing examples 2 to 24>
Toners 2 to 24 were obtained in the same manner except that the toner particles and the metal titanate fine particles used in Production Example 1 of the toner were changed as shown in Table 3. Table 3 shows the toner properties of the toners 2 to 24.

[Examples 1 to 20, Comparative Examples 1 to 4]
At the time of evaluation, a modified machine of LBP712Ci (manufactured by Canon Inc.) was used as an evaluation machine. The process speed of the main body was modified to 275 mm / sec. Then, necessary adjustments were made so that image formation was possible under these conditions. Further, the toner was filled in a predetermined cartridge in an amount of 160 g each. As the evaluation paper, CS-680 sold by Canon Marketing Japan was used.

<Poor regulation>
The evaluation of poor regulation was carried out in a low temperature and low humidity environment (temperature 15 ° C., relative humidity 10%) and an extremely low temperature environment (1 ° C.), which are severe for charge-up. Assuming a long-term durability test, the horizontal line pattern with a print rate of 1% was set as 2 sheets / job, and the machine was temporarily stopped between jobs before the next job started. In the above mode, a total of 17,000 images were subjected to an image ejection test, and images were visually confirmed by the 15,000th image every 500 images. The evaluation was made as follows according to the number of sheets until the image became uneven due to the toner that could not be regulated on the toner carrier due to poor regulation of the toner regulating member and the toner carrier.
A: No occurrence.
B: Occurs from 16001 to 17000th sheet.
C: Occurs from 15001 to 16000th.
D: Occurs up to the 15000th sheet.

<Initial cover and neglected cover 1, 2>
The evaluation of the neglected cover 1 was performed in a high-temperature and high-humidity environment (temperature 30 ° C., relative humidity 80%) in which the rising property of charging was disadvantageous. First, an all-white image was printed on a piece of paper with Post-it around the bottom center, and the density difference between the part hidden by Post-it and the part not covered by Post-it was used as the initial fog value. Assuming a long-term durability test, the horizontal line pattern with a print rate of 1% was set as 2 sheets / job, and the machine was temporarily stopped between jobs before the next job started. In this mode, a total of 15,000 image extraction tests were performed, the machine was turned off for 72 hours immediately after the 15,000 image output was completed, and the developer was left in the machine. After the machine was left unattended, the power of the machine was turned on again, an image similar to the initial fog was printed, and the density difference was set to the value of the unattended cover 1. After performing the neglected cover 1, the power of the machine was turned off for another 96 hours (168 hours in total), and the developer was left in the machine. After the machine was left unattended, the power of the machine was turned on again, an image similar to the initial fog was printed, and the density difference was set to the value of the unattended cover 2.

A reflection densitometer (reflect meter model TC-6DS manufactured by Tokyo Denshi Co., Ltd.) was used, and an amber light filter was used as the filter. The evaluation criteria were set as follows.
A: Less than 2.0 B: 2.0 or more and less than 3.0 C: 3.0 or more and less than 4.0 D: 4.0 or more

Toners 1 to 23 were evaluated by the above evaluation method. The evaluation results are shown in Table 4.

Claims (7)

Toner particles having a binder resin and a surfactant ,
Titanate metal fine particles and
Toner with
The metal titanate fine particles are
(A) Number of primary particles The average particle size is 10 nm or more and 100 nm or less.
(B) In the methanol wettability test, when the transmittance of light having a wavelength of 780 nm is 50%, the methanol concentration is 30.0% or more and 68.0% or less .
The surface of the metal titanate fine particles is treated with any two or more of the surface treatment agents having a structure represented by the following formula (1) or (2).
Toner characterized by that.

(In the formula (1), Ra to Rf represent a hydrogen atom, an alkyl group having 1 or more and 10 or less carbon atoms, or an alkyl fluoride group having 1 or more and 10 or less carbon atoms. At least one of Ra to Rf is carbon. Represents an alkyl fluoride group of number 1 or more and 10 or less.)

(In the formula (2), Rg represents an alkyl group having 1 or more and 10 or less carbon atoms or an alkyl fluoride group having 1 or more and 10 or less carbon atoms, and Rh is a hydrogen atom or an alkoxy having 1 or more and 3 or less carbon atoms. Represents a group.) The toner according to claim 1 , wherein the surfactant is an anionic surfactant. The toner according to claim 1 or 2 , wherein the surfactant has a phosphorus element or a sulfur element. The toner according to any one of claims 1 to 3, wherein the amount of the surfactant present on the surface of the toner is 10 ppm or more and 300 ppm or less. The invention according to any one of claims 1 to 4, wherein the content of the metal titanate fine particles in the toner is 0.4% by mass or more and 1.5% by mass or less based on the mass of the toner. toner. The toner according to any one of claims 1 to 5 , wherein the metal titanate fine particles are strontium titanate fine particles. Atomic intensity (TRA) derived from the surfactant measured using the toner particles as a measurement sample using X-ray photoelectron spectroscopy (ESCA), and
Atomic intensity (TRB) derived from the metal titanate fine particles measured using the toner as a measurement sample using X-ray photoelectron spectroscopy (ESCA), and
The toner according to any one of claims 1 to 6 , wherein the ratio ( TRB / TRA ) is 0.5 or more.