JP6489847B2 - Toner production method - Google Patents

Description

  The present invention relates to a method for producing toner used in electrophotography, electrostatic recording, and toner jet recording. More specifically, the present invention relates to a copying machine, which forms a toner image on an electrostatic latent image carrier and then transfers the image onto a transfer material to form a toner image and fixes the image under heat pressure to obtain a fixed image. The present invention relates to a method for producing toner used in printers and fax machines.

  In recent years, in the electrophotographic apparatus field, there has been a demand for image quality enhancement using toner. In order to improve image quality with toner, it is necessary to suppress variations in charging performance of each toner. For that purpose, it is effective to make the particle size and shape of the toner uniform, that is, to sharpen the particle size distribution, improve the aspect ratio, and reduce the fine powder ratio. The aspect ratio is the maximum length of toner particles (measured as the maximum length at two points on the contour of the particle image), the maximum length vertical length (the two straight lines parallel to the maximum length, and the particle image contour). The value is divided by the value measured as the length connecting the two straight lines vertically. In other words, the aspect ratio is one of the indexes representing the shape of the toner, and the closer to a true sphere, the closer the value is to 1. In particular, the aspect ratio is greatly increased when coalescence of a plurality of particles occurs.

  As a method for producing a toner with relatively easy particle size distribution, a resin solution in which a resin is previously dissolved in a solvent is dispersed in a dispersion medium in the presence of a dispersant, and droplets of the resin solution are formed. A “dissolution suspension method” is known in which the solvent is removed to obtain resin particles. One feature of the “dissolution suspension method” is that solid fine particles can be used as a dispersant. In addition, when a hydrophobic dispersion medium is used, a dispersant having higher hydrophobicity can be used, which is advantageous in that toner particles having excellent charge stability can be obtained.

  Patent Documents 1 and 2 propose a production method for producing resin particles using liquid or supercritical carbon dioxide as a hydrophobic dispersion medium and silica particles as inorganic fine particles as a dispersant. However, when the present inventors examined this technique, it was found that resin particles having a good particle size distribution were not necessarily obtained. The reason is that the number average diameter of the primary particles of the silica particles used is as small as about 15 nm, so that the formed droplets are easily united. Therefore, there has been a problem in further sharpening the particle size distribution.

  In recent years, with the diversification of usage environments of electrophotographic apparatuses, it has been demanded that high-quality images can be provided under various environments. At present, in order to improve the developability of the toner, it is effective to make the charge distribution of the toner uniform, and for this purpose, measures to increase the amount of external addition are taken. However, simply increasing the amount of the external additive may cause a so-called charge-up phenomenon in which the toner charge amount increases with use in a room temperature and low humidity environment, resulting in a problem that the image density decreases. In order to solve this problem, a device has been devised in which a low resistance particle such as a magnetic particle is added to a large amount of an external additive to suppress a charge-up phenomenon in a normal temperature and low humidity environment. However, when left in a high temperature and high humidity environment, there is a problem that the charge amount rise at the initial stage of printing is poor and the density becomes low. Therefore, there is still a problem in satisfying the image quality under various environments.

JP 2007-277511 A JP 2010-168522 A

  The present invention has been made in view of the above-described problems, and has a sharp particle size distribution, a low aspect ratio and a fine powder ratio, and a toner having a good initial density after standing in a high-temperature and high-humidity environment. Is to provide a method.

The present invention includes: a) a step of preparing a resin solution by mixing a binder resin, a colorant, and an organic solvent capable of dissolving the binder resin;
b) a step of forming droplets of the resin solution by mixing and granulating the resin solution and a hydrophobic dispersion medium containing organic-inorganic composite fine particles as a dispersant;
c) removing the organic solvent contained in the droplets to obtain toner particles;
In a method for producing a toner having
The organic-inorganic composite fine particles are
(1) Hydrophobized,
(2) The number average diameter is 50 nm or more and 500 nm or less,
(3) A structure in which inorganic fine particles are embedded in resin particles and the surface has a convex portion derived from the inorganic fine particles, and the presence rate of the inorganic fine particles on the surface of the organic-inorganic composite fine particles is 20% or more and 70% or less. Oh it is,
The hydrophobic dispersion medium is a high-pressure dispersion medium containing carbon dioxide.
The present invention relates to a toner manufacturing method.

  According to the present invention, it is possible to provide a method for producing a toner having a sharp particle size distribution, a low aspect ratio and a fine powder ratio, and a good initial density after standing in a high temperature and high humidity environment.

It is a figure which shows an example of the manufacturing apparatus of the manufacturing method of the toner of this invention.

The production method of the present invention is characterized by comprising the following steps a) to c).
a) A step of preparing a resin solution by mixing a binder resin, a colorant and an organic solvent capable of dissolving the binder resin.
b) A step of forming droplets of the resin solution by mixing and granulating the resin solution and a hydrophobic dispersion medium containing organic / inorganic composite fine particles as a dispersant.
c) A step of obtaining toner particles by removing the organic solvent contained in the droplets.
The steps a), b), and c) are hereinafter referred to as a resin solution preparation step, a granulation step, and a solvent removal step, respectively.

  In the resin solution preparation step in the present invention, a colorant and other additives as necessary are added to an organic solvent capable of dissolving the binder resin, and a homogenizer, a ball mill, a colloid mill, an ultrasonic disperser. Dissolve or disperse uniformly with a disperser such as

  Examples of the organic solvent include the following. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and di-n-butyl ketone; ester solvents such as ethyl acetate, butyl acetate and methoxybutyl acetate; ether solvents such as tetrahydrofuran, dioxane, ethyl cellosolve and butyl cellosolve; dimethylformamide Amide solvents such as dimethylacetamide; aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene.

  In the granulation step of the present invention, the resin solution and a hydrophobic dispersion medium containing organic / inorganic composite fine particles as a dispersant are mixed and granulated to form droplets of the resin solution.

  As the dispersion medium, an aqueous medium is generally used, but in the present invention, a hydrophobic dispersion medium is used. The hydrophobic dispersion medium means a dispersion medium that is more hydrophobic than the organic solvent, that is, has a lower polarity than the organic solvent. Examples of the hydrophobic dispersion medium include the following. Hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, hexadecane, and cyclohexane; silicone solvents such as polydimethylsiloxane; high pressure carbon dioxide.

  In the solvent removal step of the present invention, toner particles are obtained by removing the organic solvent contained in the droplets. The organic-inorganic composite fine particles form a shell phase on the surface of the toner particles obtained at this time. The method for removing the organic solvent is not particularly limited. For example, the method of distilling off the solvent while heating under reduced pressure, the method of flowing an inert gas such as nitrogen, and the hydrophobic dispersion medium A method of gradually removing the organic solvent added and transferred to the hydrophobic dispersion medium is mentioned.

(Organic inorganic composite fine particles)
The organic / inorganic composite fine particles used in the present invention will be described below.

  In the present invention, the surface of the organic-inorganic composite fine particles needs to be hydrophobized. The hydrophobic treatment may be applied to the organic / inorganic composite fine particles, or the inorganic fine particles subjected to the hydrophobic treatment may be combined with a resin. By subjecting the organic / inorganic composite fine particles to a hydrophobic treatment, the organic / inorganic composite fine particles can be easily located at the interface between the droplets and the hydrophobic dispersion medium, and the dispersion stability of the droplets can be improved.

  The inorganic fine particles used for the organic / inorganic composite fine particles or the organic / inorganic composite fine particles are preferably chemically hydrophobized with an organosilicon compound that physically adsorbs to them. As a preferred method, silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Examples of such organosilicon compounds include the following.

  Hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichloro Silane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane , Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, each bonded to a terminal Si unit Dimethylpolysiloxane containing hydroxyl groups. These are used alone or in a mixture of two or more.

  The inorganic fine particles used for the organic / inorganic composite fine particles or the organic / inorganic composite fine particles may be hydrophobized with silicone oil, or may be treated together with the hydrophobizing treatment.

As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are particularly preferred.

  Examples of the method for treating silicone oil include the following methods. A method in which silica fine particles treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. A method of spraying silicone oil onto inorganic fine particles as a base. Alternatively, it is more preferable to dissolve or disperse silicone oil in a suitable solvent, and then add and mix inorganic fine particles to remove the solvent.

  Examples of the inorganic fine particles of the organic-inorganic composite fine particles of the present invention include silica, alumina, titania, zinc oxide, strontium titanate, cerium oxide, and calcium carbonate. In particular, when the inorganic fine particles are silica, it is preferable because the chargeability is excellent and an effect on the developability is obtained. Silica may be obtained by a dry method such as fumed silica, or may be obtained by a wet method such as sol-gel silica.

  The organic-inorganic composite fine particles of the present invention need to have a number average diameter of 50 nm to 500 nm.

  The organic-inorganic composite fine particles are adsorbed on the surface of the droplets of the resin solution during granulation and serve as a dispersant for improving the dispersibility of the droplets. In order to improve the dispersibility of the droplets, it is necessary to maintain the state of being adsorbed on the surface of the toner particles until the above-described solvent removal step is completed, thereby preventing the droplets from being coalesced. For this purpose, it is necessary to use particles that are somewhat large as a dispersant. As a result of intensive studies by the present inventors, by making the number average diameter of the primary particles of the organic-inorganic composite fine particles within the above range, coalescence of droplets can be prevented, and the particle size distribution of toner particles can be sharpened. The toner produced by the production method of the present invention can exhibit high image quality.

  When the number average diameter of the organic / inorganic composite fine particles is smaller than 50 nm, the attractive force between the organic / inorganic composite fine particles and the liquid droplets is increased, so that the adsorption action is strengthened. On the other hand, since the steric repulsion between the droplets adsorbed by the organic-inorganic composite fine particles is reduced, the dispersion stabilizing action is weakened. Therefore, although the organic-inorganic composite fine particles are easily adsorbed to the droplets, since the dispersion stability of the droplets adsorbed with the organic-inorganic composite fine particles is low, coalescence occurs and the aspect ratio of the toner particles increases.

  If it is larger than 500 nm, the steric repulsion between the droplets adsorbed with the organic-inorganic composite fine particles is increased, and the dispersion stabilizing action becomes strong. On the other hand, since the attractive force between the organic-inorganic composite fine particles and the liquid droplets becomes small, the adsorption action becomes weak. Accordingly, since the organic / inorganic composite fine particles cannot be adsorbed and maintained in the droplets, the coverage of the organic / inorganic composite fine particles with respect to the droplets is reduced, the coalescence of the droplets cannot be prevented, and the particle size distribution of the toner particles is widened. . In addition, the organic / inorganic composite fine particles that could not be adsorbed and maintained in the droplets aggregate with each other to form fine powder, and as a result, the fine powder ratio increases. A more preferable number average diameter is 70 nm or more and 400 nm or less.

  The number average diameter of the organic / inorganic composite fine particles can be adjusted by changing the particle size of the inorganic fine particles used in the organic / inorganic composite fine particles or the amount ratio of the inorganic fine particles to the resin.

  The organic-inorganic composite fine particles of the present invention have a structure in which inorganic fine particles are embedded in resin fine particles and the surface has convex portions derived from the inorganic fine particles.

  The organic-inorganic composite fine particles of the present invention are prepared by preparing an aqueous dispersion of a composition containing monomers constituting inorganic fine particles and a resin component, and then adding a polymerization initiator to the aqueous dispersion to polymerize the monomers. Can be produced. By this method, organic-inorganic composite fine particles in which inorganic fine particles are uniformly present on the surface of the resin particles can be obtained.

  Another example is a method in which a solution in which a resin component is dissolved in an organic solvent is added in a state where inorganic fine particles are dispersed in an aqueous medium to form organic-inorganic composite emulsified particles. By removing the organic solvent from the emulsified particles, organic-inorganic composite fine particles in which inorganic fine particles are uniformly present on the surface of the resin particles can be obtained.

  In addition, a manufacturing method in which inorganic fine particles are implanted into resin particles later is also included. As a method for implanting inorganic fine particles into resin particles, a hybridizer (manufactured by Nara Machinery Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), mechanofusion (manufactured by Hosokawa Micron Co., Ltd.), or Hi-Flex Grall (manufactured by Earth Technica Corp.) .

In the present invention, the resin component contained in the organic / inorganic composite fine particles is preferably a resin synthesized by a silane compound represented by the following chemical formula [1].
Chemical formula [1]
X-SiH _3-n (OR) _n
Here, X represents an organic functional group, R represents a methyl or ethyl group, and n represents an integer of 1 to 3.

  In order to synthesize a resin using the silane compound represented by the chemical formula [1], the organic functional group X preferably has a polymerizable functional group such as a vinyl group, an acrylate group, or a methacrylate group. Preferred are the compounds listed below. Vinyltriacetoxysilane, (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) triethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxy Methyltriethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy Silane, vinyltris (2-methoxyethoxy) silane.

  The resin component contained in the organic-inorganic composite fine particles of the present invention preferably contains 50.0% by mass or more of a resin synthesized from a silane compound. Thereby, affinity with resin A which forms a shell phase becomes favorable.

  The resin component of the organic-inorganic composite fine particles of the present invention may contain the following resins in addition to the resin having a siloxane bond. Polystyrene, homopolymer of styrene of polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-acrylic Ethyl acid copolymer, Styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, Styrene-dimethylaminoethyl acrylate copolymer, Styrene-methyl methacrylate copolymer, Styrene-ethyl methacrylate copolymer Polymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, Styrene-butier Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer of styrene-maleic acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, Polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, polyolefin resin, polyacrylonitrile, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone, vinyl chloride-acetic acid Vinyl copolymer, straight silicone resin composed of organosiloxane bond or modified product thereof, fluorine resin, phenol resin, amino resin, benzoguanamine resin, Rear resins, polyamide resins, it is possible to use an epoxy resin, they may be used alone or in combination of plural kinds.

  In the organic-inorganic composite fine particles of the present invention, the abundance of the inorganic fine particles on the surface needs to be 20% or more and 70% or less.

  By setting the abundance of the inorganic fine particles on the surface of the organic-inorganic composite fine particles within the above range, the inorganic fine particles and the resin particle components are exposed on the surface without being excessive or insufficient. Since the resin particle component is exposed on the surface of the organic-inorganic composite fine particles, the organic-inorganic composite fine particles are easily adsorbed to the droplets during granulation, and the dispersibility of the droplets is improved.

  Further, since the inorganic fine particles are exposed on the surface of the organic-inorganic composite fine particles, the number of convex portions derived from the inorganic fine particles of the organic-inorganic composite fine particles present on the surface of the obtained toner particles increases. As a result, the chance of frictional charging between the toners increases, charging rises well even in a high temperature and high humidity environment, and the initial image density becomes good.

  When the presence ratio of the inorganic fine particles on the surface of the organic / inorganic composite fine particles is less than 20%, the number of the convex portions derived from the inorganic fine particles is reduced, or the size of the convex portions is not sufficient, so the chance of frictional charging is reduced. . For this reason, after being left in a hot and humid environment, it takes time for the charge amount to rise after the printer is started, and the initial image density is lowered.

  When the abundance ratio of the inorganic fine particles on the surface of the organic / inorganic composite fine particles exceeds 70%, the surface abundance ratio of the resin particles is relatively decreased, so that the action of adsorbing the droplets is reduced. As a result, the coverage of the organic / inorganic composite fine particles with respect to the droplets is reduced and the droplets are coalesced, so that the particle size distribution of the toner particles is widened.

  More preferably, the abundance of the inorganic fine particles is 40% or more and 60% or less.

(Binder resin)
The binder resin in the present invention will be described below. The binder resin in the present invention may contain a crystalline resin in order to easily exhibit good low-temperature fixability. The crystalline resin means a resin having a structure in which polymer molecular chains are regularly arranged. Therefore, it hardly softens to the vicinity of the melting point, but melts from the vicinity of the melting point and softens rapidly. Such a resin exhibits a clear melting point peak in differential scanning calorimetry using a differential scanning calorimeter (DSC). Examples of the crystalline resin that can be used include crystalline polyesters and crystalline alkyl resins, and crystalline polyesters are particularly preferable.

  The crystalline polyester that can be used as the binder resin in the present invention will be described.

  As the crystalline polyester, it is preferable to use an aliphatic diol having 4 to 20 carbon atoms and a polyvalent carboxylic acid as raw materials. Furthermore, the aliphatic diol is preferably a straight chain type.

  Examples of the linear aliphatic diol suitably used in the present invention include the following, but are not limited thereto. Depending on the case, it is also possible to use a mixture. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable from the viewpoint of the melting point.

  An aliphatic diol having a double bond can also be used as the aliphatic diol. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol.

  As the polyvalent carboxylic acid, an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are preferable. Among them, an aliphatic dicarboxylic acid is preferable, and a linear aliphatic dicarboxylic acid is particularly preferable.

  Examples of the aliphatic dicarboxylic acid include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Or its lower alkyl ester and acid anhydride. Of these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid or its lower alkyl ester and acid anhydride are preferred.

  Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid.

  Furthermore, a dicarboxylic acid having a double bond can also be used. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters and acid anhydrides are also included. Among these, fumaric acid and maleic acid are preferable in terms of cost.

  There is no restriction | limiting in particular as a manufacturing method of the said crystalline polyester, It can manufacture with the general polyester polymerization method which makes the said acid monomer and alcohol monomer react. For example, direct polycondensation and transesterification are used separately depending on the type of monomer.

  The production of the crystalline polyester is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. If necessary, the reaction system is reduced in pressure and reacted while removing water and alcohol generated during condensation. preferable. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point is preferably added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance and then polycondense together with the main component.

  Examples of the catalyst that can be used in the production of the crystalline polyester include the following. Titanium catalyst of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Tin catalyst of dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

  The melting point of the crystalline resin contained in the binder resin used in the present invention is preferably 50 ° C. or higher and 90 ° C. or lower. Within this range, it becomes easy to soften at the time of fixing, and good low-temperature fixability is easily obtained. When the temperature is lower than 50 ° C., the storage stability may be deteriorated. When the temperature is higher than 90 ° C., it is difficult to soften at the time of fixing, and good low-temperature fixing property is difficult to obtain.

  An amorphous resin can also be used for the binder resin in the present invention.

  The amorphous resin that can be used for the binder resin in the present invention will be described. Examples of the amorphous resin include, but are not limited to, vinyl resins such as polyurethane resins, polyester resins, styrene acrylic resins, and polystyrene. These resins may be modified with urethane, urea, or epoxy. Among these, from the viewpoint of maintaining elasticity, the polyester resin and the polyurethane resin are preferably used.

  The polyurethane resin as the amorphous resin is a reaction product of a diol component and a diisocyanate component containing a diisocyanate group, and resins having various functions can be obtained by adjusting the diol component and the diisocyanate component.

  Examples of the diisocyanate component include the following. C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, and these diisocyanates Modified product (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, hereinafter also referred to as modified diisocyanate), and two or more of these Mixture of.

  Examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate.

  Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate.

  Of these, preferred are HDI, IPDI, and XDI.

  Examples of the diol component include the following. Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol), alkylene ether glycol (polyethylene glycol, polypropylene glycol) alicyclic diol (1,4-cyclohexanedimethanol), bisphenols (bisphenol A) ), An alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol. The alkyl part of the alkylene glycol and alkylene ether glycol may be linear or branched.

  Examples of the monomer used for the polyester resin as the amorphous resin include divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols. Specific examples of these monomer components include the following compounds. Divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid dibasic acid, anhydrides thereof and lower alkyl esters thereof, maleic acid , Fumaric acid, itaconic acid, citraconic acid aliphatic unsaturated dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the divalent alcohol include the following compounds. Bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol. Examples of the trivalent or higher alcohols include the following compounds. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol. These may be used individually by 1 type and may use 2 or more types together. If necessary, a monovalent acid such as acetic acid or benzoic acid, or a monovalent alcohol such as cyclohexanol or benzyl alcohol can be used for the purpose of adjusting the acid value or the hydroxyl value.

  The polyester resin as the amorphous resin can be synthesized by a conventionally known method using the monomer component.

  The glass transition temperature (Tg) of the amorphous resin in the binder resin is preferably 50 ° C. or higher and 130 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. By being in this range, the elasticity in the fixing region is easily maintained.

  In the present invention, when the crystalline resin is used for the binder resin, the ratio of the crystalline resin to the amorphous resin in the binder resin is 30.0% by mass or more and 85. It is preferable that it is 0 mass% or less. When the amount of the crystalline resin is less than 30.0% by mass, it becomes difficult to soften at the time of fixing, and it becomes difficult to obtain good low-temperature fixability. On the other hand, when the amount is more than 85.0% by mass, the elasticity after melting the toner is difficult to be maintained, and the fixing region tends to be narrowed. More preferably, it is 50.0 mass% or more.

  Further, in the present invention, it is also preferable to use a block polymer in which a portion that can take a crystal structure, that is, a crystalline resin component, and a portion that cannot take a crystal structure, that is, an amorphous resin component are chemically bonded. One of the forms.

  The block polymer is composed of an AB type diblock polymer, an ABA type triblock polymer, a BAB type triblock polymer, an ABAB... Type multi of the crystalline resin component (A) and the amorphous resin component (B). Any form of block polymer can be used.

  In the present invention, as a method for preparing the block polymer, a component for forming a crystal part composed of the crystalline resin component and a component for forming an amorphous part composed of the amorphous resin component are separately prepared, A method of combining the two (two-step method), a method of preparing raw materials of a component for forming a crystal part and a component for forming an amorphous part at the same time (one-step method) can be used.

  The block polymer in the present invention can be selected from various methods in consideration of the reactivity of each terminal functional group to be the block polymer.

  When both the crystalline resin component and the amorphous resin component are polyester resins, they can be prepared by preparing each component separately and then bonding them using a binder. In particular, when one of the polyesters has a high acid value and the other polyester has a high hydroxyl value, the reaction proceeds smoothly. The reaction temperature is preferably about 200 ° C.

  When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.

  On the other hand, when the crystalline resin component is the crystalline polyester and the amorphous resin component is the polyurethane resin, after preparing each component separately, the alcohol terminal of the crystalline polyester and the isocyanate terminal of the polyurethane Can be prepared by urethanization reaction. The synthesis can also be performed by mixing and heating the crystalline polyester having an alcohol terminal and the diol and diisocyanate constituting the polyurethane resin. At the initial stage of the reaction when the diol and diisocyanate concentrations are high, the diol and diisocyanate react selectively to form a polyurethane resin, and after the molecular weight has increased to some extent, the urethanization reaction between the isocyanate terminal of the polyurethane resin and the alcohol terminal of the crystalline polyester occurs. The block polymer can be used.

  The ratio of the crystalline resin component in the block polymer is preferably 30.0% by mass or more and 85.0% by mass or less.

(wax)
The toner particles used in the toner of the present invention preferably contain a wax. The wax is not particularly limited, and examples thereof include the following.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  Waxes particularly preferably used in the present invention are aliphatic hydrocarbon waxes and ester waxes. The ester wax used in the present invention is preferably a tri- or higher functional ester wax, more preferably a tetra-functional or higher ester wax, and particularly preferably a hexa-functional or higher functional ester wax.

  The tri- or higher functional ester wax is obtained, for example, by condensation of a tri- or higher functional acid and a long-chain linear saturated alcohol, or synthesis of a tri- or higher-functional alcohol and a long-chain linear saturated fatty acid.

  Examples of the trifunctional or higher functional alcohol that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol. Further, as these condensates, so-called polyglycerin such as diglycerin condensed with glycerin, triglycerin, tetraglycerin, hexaglycerin and decaglycerin, ditrimethylolpropane condensed with trimethylolpropane, tristrimethylolpropane and pentaerythritol Examples thereof include condensed dipentaerythritol and trispentaerythritol. Among these, a structure having a branched structure is preferable, pentaerythritol or dipentaerythritol is more preferable, and dipentaerythritol is particularly preferable.

The long-chain linear saturated fatty acid that can be used in the present invention is represented by the general formula C _n H _{2n + 1} COOH, and those in which n is 5 or more and 28 or less are preferably used.

  For example, the following can be mentioned, but the present invention is not limited thereto. Depending on the case, it is also possible to use a mixture. Examples include caproic acid, caprylic acid, octylic acid, nonylic acid, decanoic acid, dodecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and behenic acid. From the viewpoint of the melting point of the wax, myristic acid, palmitic acid, stearic acid, and behenic acid are preferred.

  Examples of the trifunctional or higher functional acid that can be used in the present invention include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Trimellitic acid, butanetetracarboxylic acid.

The long-chain linear saturated alcohol that can be used in the present invention is represented by C _n H _{2n + 1} OH, and those having n of 5 or more and 28 or less are preferably used.

  For example, the following can be mentioned, but the present invention is not limited thereto. Depending on the case, it is also possible to use a mixture. Examples include capryl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol. From the viewpoint of the melting point of the wax, myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol are preferable.

  In the present invention, the wax content in the toner is preferably 1.0% by mass or more and 20.0% by mass or less, more preferably 2.0% by mass or more and 15.0% by mass. When the amount is less than 1.0% by mass, the toner releasability tends to be reduced, and the transfer paper is likely to be wound when the fixing body is at a low temperature. When the amount is more than 20.0% by mass, the wax tends to be exposed on the toner surface, and the heat resistant storage stability tends to be lowered.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower as measured by a differential scanning calorimeter (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less. When the maximum endothermic peak is lower than 60 ° C., the wax tends to be exposed on the toner surface and the heat resistant storage stability tends to be lowered. On the other hand, when the maximum endothermic peak is higher than 120 ° C., it becomes difficult for the wax to melt properly at the time of fixing, and the low-temperature fixing property and the offset resistance tend to be lowered.

(Coloring agent)
The toner of the present invention contains a colorant. Examples of the colorant preferably used in the present invention include organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic powder. In addition, it is possible to use colorants conventionally used in toners. I can do it.

  Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. 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 are preferably used.

  Examples of the colorant for cyan include the following. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.

  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 1.0% by mass or more and 20.0% by mass or less to the toner. When magnetic powder is used as the colorant, the amount added is preferably 40.0% by mass or more and 150.0% by mass or less based on the toner.

(Charge control agent)
In the toner of the present invention, a charge control agent may be contained in the toner particles as necessary. Further, the toner particles may be externally added. 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.

  A known charge control agent can be used as the charge control agent, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Examples of controlling the toner to be positively charged include the following. Examples include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds and imidazole compounds.

  A preferable blending amount of the charge control agent is 0.01% by mass or more and 20.0% by mass or less, and more preferably 0.5% by mass or more and 10.0% by mass or less with respect to the toner.

  In this invention, it is preferable that the addition amount of the said organic inorganic composite fine particle with respect to 100 mass parts of said binder resin is 2.5 to 25.0 mass parts. In order for the organic / inorganic composite fine particles to function as a dispersant, it is necessary that the organic / inorganic composite fine particles cover 100% of the droplets. In this case, the amount of the organic / inorganic composite fine particles added to the binder resin depends on the desired particle size of the toner particles and the organic / inorganic composite fine particles, and an appropriate range is 2.5 parts by mass or more and 25.0 masses. Equivalent to less than

(Toner production method)
The production method of the present invention is particularly preferably a production method using high-pressure carbon dioxide as a hydrophobic dispersion medium.

  That is, in the present invention, a resin composition in which a binder resin and a colorant are dissolved or dispersed in a medium containing an organic solvent, a dispersion containing carbon dioxide in a high-pressure state containing organic-inorganic composite fine particles. A production method in which toner particles are formed by dispersing in a medium and removing the organic solvent from the obtained dispersion is preferred.

  Here, the high-pressure carbon dioxide is preferably carbon dioxide having a pressure of 1.5 MPa or more. Further, liquid or supercritical carbon dioxide may be used alone as a dispersion medium, and an organic solvent may be contained as another component. In this case, it is preferable that the high-pressure carbon dioxide and the organic solvent form a homogeneous phase.

  Hereinafter, a method for producing toner particles using a dispersion medium containing carbon dioxide in a high-pressure state suitable for the production method of the present invention will be described as an example.

  First, in the resin solution preparation step, a colorant, wax, and other additives as necessary are added to an organic solvent capable of dissolving the binder resin, and a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser is added. It is uniformly dissolved or dispersed by a disperser.

  Next, in the granulation step, the resin solution thus obtained and high-pressure carbon dioxide are mixed to form droplets of the resin solution.

  At this time, it is necessary to disperse the organic-inorganic composite fine particles as a dispersant in a dispersion medium containing high-pressure carbon dioxide.

  As the dispersant, for example, other resin fine particles may be used in combination.

  As the resin constituting the resin fine particles, either a crystalline resin or an amorphous resin can be used.

  Examples of the crystalline resin that can be used for the resin fine particles include crystalline polyesters and crystalline alkyl resins. As the monomer used for the crystalline polyester, a monomer that can be used for the above-described binder resin is preferably used.

  The melting point of the crystalline polyester in the resin fine particles of the present invention is preferably 50 ° C. or higher and 120 ° C. or lower, and more preferably 50 ° C. or higher and 90 ° C. or lower in consideration of melting at the fixing temperature.

  Examples of the amorphous resin that can be used for the resin fine particles include, but are not limited to, vinyl resins such as polyurethane resins, polyester resins, styrene acrylic resins, and polystyrene. These resins may be modified with urethane, urea, or epoxy.

  The polyester resin as the amorphous resin is preferably a resin that can be used as the resin fine particles described above. As the polyurethane resin as the amorphous resin, a resin that can be used for the resin fine particles described above is preferably used.

  The glass transition temperature (Tg) of the amorphous resin in the resin fine particles of the present invention is preferably 50 ° C. or higher and 130 ° C. or lower. More preferably, it is 50 degreeC or more and 100 degrees C or less.

  The weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the resin fine particles in the present invention is preferably 20,000 or more and 80,000 or less. By being in this range, the shell phase has an appropriate hardness and durability is improved. If it is smaller than 20,000, the durability tends to be lowered, and if it is larger than 80,000, the fixability may be lowered.

  Moreover, you may use together the dispersion stabilizer of a liquid state. Examples of the dispersion stabilizer include various surfactants having a high affinity for carbon dioxide, such as the above-mentioned organic polysiloxane structure and fluorine-containing compounds, nonionic surfactants, anionic surfactants, and cationic surfactants. It is done. These dispersion stabilizers are discharged out of the system together with carbon dioxide in a solvent removal step described later. Therefore, after the toner particles are produced, the amount remaining in the toner particles is extremely small.

  In the present invention, any method may be used for dispersing the dispersant in a dispersion medium containing carbon dioxide in a high pressure state. Specific examples include a method in which a dispersion medium containing the dispersant and high-pressure carbon dioxide is charged into a container and directly dispersed by stirring or ultrasonic irradiation. Another example is a method in which a dispersion liquid in which the dispersant is dispersed in an organic solvent is introduced into a container charged with a dispersion medium containing carbon dioxide in a high-pressure state using a high-pressure pump.

  In the present invention, any method may be used as a method of dispersing the resin composition in a dispersion medium containing carbon dioxide in a high pressure state. As a specific example, there is a method of introducing the resin composition into a container containing a dispersion medium containing high-pressure carbon dioxide in a state where the dispersant is dispersed, using a high-pressure pump. Moreover, a dispersion medium containing carbon dioxide in a high-pressure state in which the dispersant is dispersed may be introduced into a container charged with the resin composition.

  In the present invention, it is important that the dispersion medium containing carbon dioxide in a high-pressure state is a single phase. When granulating by dispersing the resin composition in carbon dioxide in a high pressure state, a part of the organic solvent in the droplets moves into the dispersion. At this time, it is not preferable that the carbon dioxide phase and the organic solvent phase exist in a separated state, which causes a drop in the stability of the droplets. Therefore, it is preferable to adjust the temperature and pressure of the dispersion medium and the amount of the resin composition with respect to the high-pressure carbon dioxide within a range in which the carbon dioxide and the organic solvent can form a homogeneous phase.

  In addition, regarding the temperature and pressure of the dispersion medium, attention should be paid to granulation properties (ease of forming droplets) and solubility of constituent components in the resin composition in the dispersion medium. For example, the binder resin and wax in the resin composition may be dissolved in the dispersion medium depending on temperature conditions and pressure conditions. Usually, the lower the temperature and the lower the pressure, the more the solubility of the above components in the dispersion medium is suppressed, but the formed droplets are likely to agglomerate and coalesce, and the granulation property is lowered. On the other hand, although the granulation property is improved as the temperature and pressure are increased, the component tends to be easily dissolved in the dispersion medium. Therefore, in the production of the toner particles of the present invention, the temperature of the dispersion medium is preferably in the temperature range of 10 ° C. or higher and 40 ° C. or lower.

  Further, the pressure in the container forming the dispersion medium is preferably 1.5 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. In addition, the pressure in this invention shows the total pressure, when components other than a carbon dioxide are contained in a dispersion medium.

  After granulation is completed in this way, in the solvent removal step, the organic solvent remaining in the droplets is removed through a dispersion medium of carbon dioxide in a high pressure state. Specifically, carbon dioxide in a high-pressure state is further mixed with the dispersion medium in which droplets are dispersed, and the remaining organic solvent is extracted into a carbon dioxide phase. By replacing with carbon dioxide in the state.

  In the mixing of the dispersion medium and the high-pressure carbon dioxide, carbon dioxide having a higher pressure may be added to the dispersion medium, and the dispersion medium may be added to carbon dioxide having a lower pressure. Also good.

  And as a method of substituting the carbon dioxide containing an organic solvent with the carbon dioxide of a high pressure state, the method of distribute | circulating a high pressure carbon dioxide is mentioned, keeping the pressure in a container constant. At this time, the toner particles formed are captured while being captured by a filter.

  When the replacement with carbon dioxide in the high-pressure state was not sufficient and the organic solvent remained in the dispersion medium, it was dissolved in the dispersion medium when the container was decompressed to recover the obtained toner particles. In some cases, the organic solvent may condense and the toner particles may be redissolved or the toner particles may coalesce. Therefore, the replacement with carbon dioxide in the high pressure state needs to be performed until the organic solvent is completely removed. The amount of high-pressure carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and most preferably 1 to 30 times the volume of the dispersion medium.

  When removing the toner particles from the dispersion containing high-pressure carbon dioxide in which the toner particles are dispersed, the container may be decompressed to room temperature and normal pressure at once. The pressure may be reduced stepwise by providing. The decompression speed is preferably set within a range where the toner particles do not foam.

  The organic solvent and carbon dioxide used in the present invention can be recycled.

  The toner particles of the present invention preferably have a weight average particle diameter (D4) of 3.00 μm or more and 8.00 μm or less. More preferably, they are 5.00 micrometers or more and 7.00 micrometers or less. It is preferable to use toner particles having such a weight average particle diameter (D4) in order to sufficiently satisfy the dot reproducibility while improving the handleability.

  The toner of the present invention has a number average molecular weight (Mn) of 8,000 to 40,000 and a weight average molecular weight (Mw) of 15,0 in gel permeation chromatography (GPC) measurement of tetrahydrofuran (THF) solubles. It is preferably from 000 to 60,000. By being in this range, it is possible to impart appropriate viscoelasticity to the toner. If Mn is less than 8,000 and Mw is less than 15,000, the toner becomes too soft and the heat-resistant storage stability tends to decrease. Further, the toner is easily peeled from the fixed image. If Mn is larger than 40,000 and Mw is larger than 60,000, the toner becomes too hard and the fixability tends to be lowered. A more preferable range of Mn is 10,000 or more and 20,000 or less, and a more preferable range of Mw is 20,000 or more and 50,000 or less. Furthermore, it is desirable that Mw / Mn is 6 or less. A more preferable range of Mw / Mn is 3 or less.

  Measurement methods for various physical properties of the toner and toner material of the present invention will be described below.

<Method for measuring number average diameter of organic / inorganic composite fine particles, resin fine particles and inorganic fine particles>
The number average diameter of the organic / inorganic composite fine particles, resin fine particles, and inorganic fine particles is observed using a scanning electron microscope S4700 (manufactured by Hitachi, Ltd.), the particle size of 100 particles is measured, and the average value is determined as the primary particle. Was the number average diameter.

<Method for measuring the abundance of inorganic fine particles on the surface of organic / inorganic composite fine particles>
The abundance ratio of the inorganic fine particles on the surface of the organic / inorganic composite fine particles is measured by ESCA (X-ray photoelectron spectroscopy). When the inorganic fine particles are silica particles, it is calculated from the atomic weight of silicon derived from silica (hereinafter abbreviated as Si). Is done. ESCA is an analysis method for detecting atoms in a region of several nm or less in the depth direction of the sample surface. Therefore, it is possible to detect atoms on the surface of the organic / inorganic composite fine particles.

  As a sample holder, a 75 mm square platen (provided with a screw hole of about 1 mm diameter for fixing the sample) attached to the apparatus was used. Since the screw hole of the platen penetrates, the hole is filled with resin, and a recess for measuring powder having a depth of about 0.5 mm is created. The measurement sample was packed into the concave portion with a spatula, and the sample was prepared by grinding.

The ESCA apparatus and measurement conditions are as follows.
Equipment used: Quantum 2000 manufactured by ULVAC-PHI
Analysis method: Narrow analysis Measurement conditions:
X-ray source: Al-Kα
X-ray conditions: 100μ25W15kV
Photoelectron capture angle: 45 °
PassEnergy: 58.70eV
Measurement range: φ100μm

  Measurement was performed under the above conditions.

  The analysis method first corrects the peak derived from the C—C bond of the carbon 1s orbital to 285 eV. Then, from the peak area derived from the silicon 2p orbit where the peak top is detected at 100 eV or more and 105 eV or less, the relative sensitivity factor provided by ULVAC-PHI is used to calculate the amount of Si derived from silica relative to the total amount of constituent elements. To do.

  First, organic-inorganic composite fine particles are measured. Moreover, the particle | grains of the inorganic component used when producing organic-inorganic composite fine particles by the same method are measured. When the inorganic component is silica, the ratio of “Si amount when measuring organic / inorganic composite fine particles” to “Si amount when measuring silica particles” is the presence of the inorganic fine particles on the surface of the organic / inorganic composite fine particles in the present invention. Rate. In this measurement, calculation was performed using sol-gel silica particles (number average particle diameter 110 nm) as silica particles.

  The method for separating the organic / inorganic composite fine particles from the toner can be performed, for example, by the method described in the method for quantifying organic / inorganic composite fine particles and inorganic fine particles in the toner.

  Although the case where the inorganic fine particles are silica particles has been described, when the inorganic fine particles are not silica particles, the metal species included in the inorganic fine particles are identified from the database attached to the measuring apparatus, It is only necessary to perform a focused analysis.

  The existence ratio of the inorganic fine particles on the surface of the organic / inorganic composite fine particles is observed with a transmission electron microscope “H-800” (manufactured by Hitachi, Ltd.). Set the observation conditions to be clear and observe. Under that condition, 100 observations were made. Using the obtained projection image, the area ratio (area%) of the portion derived from the inorganic fine particles was calculated. Image processing software Image-Pro Plus 5.1J (manufactured by Media Cybernetics) was used for the area% of the portion derived from the inorganic fine powder particles.

<Method for measuring the amount of Si derived from polysiloxane in organic-inorganic composite fine particles by solid-state NMR>
The amount of Si derived from polysiloxane in the organic / inorganic composite fine particles can be determined from the atomic peak area by ²⁹ Si-NMR. 10 mg of organic / inorganic composite fine particles are put in a sample tube, set in “CMX-300” manufactured by Chemanetics, and measured. Among the obtained signals, a peak near 100 ppm (having a peak at 85 ppm to 115 ppm) is attributed to a peak derived from SiO _2, and a peak near 65 ppm (having a peak at 50 ppm to 80 ppm) is poly. The amount of Si derived from polysiloxane (atomic%) was determined from the siloxane-derived peak and the area ratio.

The measurement conditions for solid-state NMR in the present invention are as follows.
Apparatus: “CMX-300” manufactured by Chemagnetics
Temperature: 25 ° C
Reference substance: HMB (external standard: 17.35 ppm)
Measurement nucleus: 13C nuclear pulse width: 4.5 μsec (90 ° pulse)
Pulse repetition time: ACQTM 34.13msec
PD = 5sec (CP / MAS)
Data points: POINT 8192, SAMPO 1024
Spectrum width: 30.03 kHz
Pulse mode: CP / MAS
Sample rotation speed: 4 kHz
Contact time: 1.5msec

<Measurement method of particle diameter of colorant particle and wax particle>
The particle diameters of the colorant particles and the wax particles are measured using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.) in the range of 0.001 μm to 10 μm, and the volume average particle diameter (μm Or nm). In addition, water was selected as a dilution solvent.

<Measuring method of melting point of crystalline polyester, block polymer, and wax>
Melting | fusing point of crystalline polyester, block polymer, and wax was measured on condition of the following using DSC Q1000 (made by TA Instruments).
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 200 ° C

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in a silver pan, and measured using an empty silver pan as a reference. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 20 ° C., and then heated again. In the case of crystalline polyester and block polymer, the peak temperature of the maximum endothermic peak of the DSC curve in the temperature range of 20 ° C. to 200 ° C. is measured in the first temperature rising process, and in the case of wax in the second temperature rising process. The melting point of polyester, block polymer, and wax.

<Measuring method of number average molecular weight (Mn) and weight average molecular weight (Mw) of crystalline polyester and block polymer>
In the present invention, the molecular weights (Mn, Mw) of the crystalline polyester and block polymer soluble in tetrahydrofuran (THF) are measured by GPC as follows.

First, a sample is dissolved in THF at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Method for Measuring Toner Particle Aspect Ratio and Fine Powder Ratio>
The aspect ratio and fine powder ratio of the toner particles are measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between 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. Further, 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 is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, The maximum length (D _max ), the maximum length vertical length (D _v-max ), and the projected area (S) are measured.

The maximum length (D _max ) of the particle image is a value measured as the maximum length at two points on the contour of the particle image, and the maximum vertical length (D _v-max ) is the maximum length (D _v-max ) is a value measured as the shortest length connecting two straight lines vertically when the particle image contour is sandwiched between two straight lines.

The aspect ratio is obtained using the maximum length (D _max ) and the maximum length vertical length (D _v-max ). The aspect ratio is defined as a value obtained by dividing the maximum length ( _Dmax ) by the maximum length vertical length ( _Dv-max ), and is calculated by the following equation.
Aspect ratio = D _max / D _v-max

  The aspect ratio approaches 1 when there is little coalescence between particles and the particle image is more circular, the more the coalescence between particles, and the higher the acicularity of the particle image, the larger the aspect ratio becomes.

The equivalent circle diameter is determined using the area S. The equivalent circle diameter is a diameter of a circle having the same area as the projected area of the particle image, and is calculated by the following equation.
Equivalent circle diameter (μm) = 2 × (π × S) ^1/2

Next, the fine powder ratio is determined using the number of toner particles having an equivalent circle diameter of less than 1.985 μm (N _s ) and the number of all toner particles (N _all ). The fine powder is defined as particles having an equivalent circle diameter of less than 1.985 μm. The fine powder rate is calculated by the following equation.
Fine powder ratio (number%) = N _s / N _all × 100

  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 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.

The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. 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 a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the maximum length (D _max ) and maximum length vertical length ( D _v-max ) and the projected area (S) are obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “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 diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner particles>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner particles are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman・ Set the value obtained using Coulter). By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. 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 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte solution (5) in which the toner particles are dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way.

<Synthesis of crystalline polyester 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Sebacic acid 124.0 parts by mass-1,6-hexanediol 76.0 parts by mass-Dibutyltin oxide 0.1 part by mass The system was purged with nitrogen by depressurization, and then stirred at 180 ° C for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and the temperature was further maintained for 2 hours. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. The melting point of the crystalline polyester 1 was 73 ° C., Mn was 5,800, and Mw was 11,800.

<Synthesis of crystalline polyester 2>
In the synthesis of crystalline polyester 1, the same procedure was followed except that the amount of sebacic acid charged was changed to 121.0 parts by mass and the amount of 1,6-hexanediol charged was changed to 79.0 parts by mass. Got. The melting point of the crystalline polyester 2 was 73 ° C., Mn was 2,500, and Mw was 4,600.

<Synthesis of block polymer>
Crystalline polyester 1 180.0 parts by mass Xylylene diisocyanate (XDI) 73.0 parts by mass Cyclohexanedimethanol (CHDM) 47.0 parts by mass Tetrahydrofuran (THF) 300.0 parts by mass A stirrer and a thermometer The above was charged into a reaction vessel equipped with nitrogen substitution. The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours. The solvent THF was distilled off to obtain a block polymer. The melting point of the block polymer was 65 ° C., Mn was 12,300, and Mw was 30,400.

<Preparation of block polymer solution>
A beaker equipped with a stirrer was charged with 500.0 parts by mass of acetone and 500.0 parts by mass of a block polymer, and stirring was continued until the solution was completely dissolved at a temperature of 40 ° C. to prepare a block polymer solution.

<Example of production of organic-inorganic composite fine particles 1>
In a 250 mL four-necked round bottom flask equipped with a stirring motor, a condenser, and a thermocouple, 18.7 g of an aqueous dispersion of colloidal silica having a number average particle diameter of 25 nm (silica concentration: 40% by mass), 125 mL of ion-exchanged water, and 56.1 g of methacryloxypropyl-trimethoxysilane (MPS) was added. The mixture was heated to 65 ° C. with stirring at 120 rpm. Nitrogen was blown into the mixture for 30 minutes, and after 3 hours, 0.16 g of a radical initiator 2,2′-azobisisobutyronitrile (abbreviated as AIBN) dissolved in 10 mL of ethanol was added, and the temperature was set to 75 ° C. did. Radical polymerization was performed at 75 ° C. for 5 hours, and then 3 mL (2.3 g) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) was added to the mixture. The reaction was further carried out for 3 hours, and the mixture was filtered through a 170 mesh sieve to remove aggregates, transferred to a stainless steel tray, and then dried at 120 ° C. for 12 hours. A white powdery solid was collected and pulverized for 1 minute using an oster blender OB-1 to obtain organic-inorganic composite fine particles 1. The volume was set to 250 ml and the rotation was set to 15700 rpm. Table 1 shows the physical properties of the organic-inorganic composite fine particles 1.

<Production example of organic-inorganic composite fine particles 2 to 14>
In the production example of the organic-inorganic composite fine particles 1, except that the addition amount of methacryloxypropyl-trimethoxysilane, the type of colloidal silica, and the addition amount shown in Table 1 are changed, the organic-inorganic composite fine particles 2 to 14 are similarly prepared. Obtained. Table 1 shows the physical properties of the organic-inorganic composite fine particles 2 to 14.

<Preparation of organic-inorganic composite fine particle dispersions 1 to 14>
For organic / inorganic composite fine particles 1 to 14, 200.0 parts by mass were added to a container charged with 800.0 parts by mass of acetone while stirring, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (Nikka Bio Bios) was added. For 5 minutes to obtain organic-inorganic composite fine particle dispersions 1 to 14.

<Preparation of resin fine particle dispersion>
-75.0 parts by weight of behenyl acrylate-15.0 parts by weight of methyl methacrylate (MMA)-10.0 parts by weight of methacrylic acid (MAA)-0.3 parts by weight of azobismethoxydimethylvaleronitrile-50.0 THF Part by mass A beaker was charged with the above, stirred and mixed at 20 ° C. to prepare a monomer solution, which was introduced into a dripping funnel that had been heated and dried in advance. Separately from this, 100 parts by mass of THF was charged into a heat-dried two-necked flask. After substituting with nitrogen, a dropping funnel was attached, and the monomer solution was added dropwise at 70 ° C. for 1 hour in a sealed state. Stirring was continued for 3 hours from the end of the dropping, and a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 20.0 parts by mass of THF was added again, followed by stirring at 70 ° C. for 3 hours to obtain a reaction mixture. .

  Subsequently, the reaction mixture is dropped in 400.0 parts by mass of acetone adjusted to 20 ° C. with stirring at 4000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) over 10 minutes, whereby resin fine particles are added. A dispersion was obtained. Acetone was added to a solid content concentration of 20.0% by mass to prepare a resin fine particle dispersion. The obtained resin fine particle dispersion was dried and the number average diameter was measured. Table 1 shows the physical properties of the resin fine particles.

<Preparation of inorganic fine particles>
In a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 456.5 parts by mass of methanol, 42.0 parts by mass of pure water, and 47.1 parts by mass of 28% by mass ammonia water were mixed. The obtained solution was adjusted to 35 ° C., and 1100.0 parts by mass of tetramethoxysilane and 395.2 parts by mass of 5.4% by mass ammonia water were begun simultaneously with stirring. Tetramethoxysilane was added dropwise over 7 hours and ammonia water over 6 hours. Even after the completion of the dropping, the mixture was further stirred for 0.2 hours for hydrolysis to obtain a methanol-water dispersion of spherical sol-gel silica fine particles. Thereafter, the dispersion was sufficiently dried at 80 ° C. under reduced pressure to obtain inorganic fine particles before treatment.

  Subsequently, 100.0 parts by mass of inorganic fine particles before treatment are placed in a reaction vessel, and 37.8 parts by mass of silicone oil (KF-96, 50 cs: manufactured by Shin-Etsu Chemical Co., Ltd.) is stirred while stirring in a nitrogen atmosphere. A solution diluted with 8 parts by mass of normal hexane was sprayed. Thereafter, this mixture was stirred and dried in a stream of nitrogen at 300 ° C. for 60 minutes, cooled, and the number average diameter was measured. Table 1 shows the physical properties of the inorganic fine particles.

<Preparation of inorganic fine particle dispersion>
In a container charged with 800.0 parts by mass of acetone, 200.0 parts by mass of inorganic fine particles are added with stirring, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Machine Bios) is used for 5 minutes. By dispersing, an inorganic fine particle dispersion was obtained.

<Preparation of colorant dispersion>
・ C. I. Pigment Blue 15: 3 100.0 parts by mass, acetone 150.0 parts by mass, glass beads (1 mm) 300.0 parts by mass The above materials are put into a heat-resistant glass container, and a paint shaker (manufactured by Toyo Seiki) for 5 hours. Dispersion was performed, glass beads were removed with a nylon mesh, and a colorant dispersion having a volume average particle size of 200 nm and a solid content of 40% by mass was obtained.

<Preparation of wax dispersion>
Paraffin wax HNP10 (melting point: 75 ° C., Nippon Seiwa Co., Ltd.) 16.0 parts by mass Nitrile group-containing styrene acrylic resin 8.0 parts by mass (styrene 60 parts by mass, n-butyl acrylate 30 parts by mass, acrylonitrile 10 parts by mass Copolymer having a component as a component, peak molecular weight 8500)
Acetone 76.0 parts by mass The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 70 ° C. to dissolve paraffin wax in acetone.

  Then, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.

  This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker to obtain a wax dispersion having a volume average particle size of 270 nm and a solid content of 16% by mass.

[Example 1]
(Manufacture of toner particles 1)
In the apparatus shown in FIG. 1, first, the valves V1 and V2 and the pressure adjusting valve V3 are closed, and the organic-inorganic composite fine particle dispersion is placed in a pressure-resistant granulation tank T1 having a filter and a stirring mechanism for capturing toner particles. 1: 25.0 parts by mass were charged, and the internal temperature was adjusted to 25 ° C. Next, the valve V1 was opened, carbon dioxide (purity 99.99%) was introduced into the granulation tank T1 from the cylinder B1 using the pump P1, and the valve V1 was closed when the internal pressure reached 2.0 MPa. Meanwhile, the resin solution tank T2 was charged with a block polymer solution, a wax dispersion, a colorant dispersion, and acetone, and the internal temperature was adjusted to 25 ° C.

  Next, the valve V2 is opened and the contents of the resin solution tank T2 are introduced into the granulation tank T1 using the pump P2 while stirring the inside of the granulation tank T1 at 1000 rpm. Valve V2 was closed. After the introduction, the internal pressure of the granulation tank T1 was 5.0 MPa.

In addition, the material preparation amount (mass ratio) to the resin solution tank T2 is as follows.
Block polymer solution 100.0 parts by weight Wax dispersion 20.0 parts by weight Colorant dispersion 8.0 parts by weight Acetone 20.0 parts by weight Carbon dioxide 160.0 parts by weight

  The mass of the introduced carbon dioxide was calculated using a mass flow meter.

  After the introduction of the contents of the resin solution tank T2 to the granulation tank T1, granulation was performed by further stirring at 1000 rpm for 3 minutes.

  Next, the valve V1 was opened, and carbon dioxide was introduced into the granulation tank T1 from the cylinder B1 using the pump P1. At this time, the pressure regulating valve V3 was set to 10.0 MPa, and carbon dioxide was further circulated while maintaining the internal pressure of the granulation tank T1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the solvent recovery tank T3, and the organic solvent and carbon dioxide were separated.

  The introduction of carbon dioxide into the granulation tank T1 was stopped when it reached 15 times the mass of carbon dioxide initially introduced into the granulation tank T1. At this point, the operation of replacing carbon dioxide containing an organic solvent with carbon dioxide containing no organic solvent was completed.

  Further, the pressure regulating valve V3 was opened little by little, and the internal pressure of the granulation tank T1 was reduced to atmospheric pressure, whereby the toner particles 1 captured by the filter were collected. D1 of toner particles 1 was 5.77 μm, D4 was 6.06 μm, and D4 / D1 was 1.05.

(Preparation of Toner 1)
With respect to 100.0 parts by mass of the toner particles 1, 1.8 parts by mass of hydrophobic silica fine powder treated with hexamethyldisilazane (number average diameter of primary particles: 7 nm), rutile type titanium oxide fine powder 0. 15 parts by mass (number average diameter of primary particles: 30 nm) was dry-mixed for 5 minutes with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 1 of the present invention.

[Examples 2 to 9]
In Example 1, the toner 2 of the present invention was used in the same manner as in Example 1 except that the type of organic-inorganic composite fine particles and the charged amount of the fine particle dispersion in the production process of the toner particles 1 were changed to those shown in Table 2. Thru 9 were obtained.

[Comparative Examples 1 to 5]
Comparative toners 1 to 5 were obtained in the same manner as in Example 1 except that the type and amount of organic-inorganic composite fine particles in the production process of toner particles 1 were changed to those shown in Table 2. It was.

[Comparative Example 6]
In Example 1, the organic-inorganic composite fine particles in the production process of the toner particles 1 were changed to resin fine particles, and the charge amount of the resin fine particles was changed to the one shown in Table 2 for comparison purposes. Toner 6 was obtained.

[Comparative Example 7]
In Example 1, the organic-inorganic composite fine particles in the production process of the toner particles 1 were changed to inorganic fine particles, and the amount of the inorganic fine particles was changed to that shown in Table 2, and the same as in Example 1 for comparison. Toner 7 was obtained.

<Evaluation of toner>
The obtained toners 1 to 9 and comparative toners 1 to 7 were measured for particle size distribution, aspect ratio, and fine powder rate according to the methods described above. Further, the initial concentration after being left in a high temperature and high humidity environment was evaluated according to the following method.

<Initial concentration after leaving in a hot and humid environment>
A commercially available Canon printer LBP9200C was used to evaluate the initial density after leaving in a high temperature and high humidity environment. The LBP 9200C employs one-component contact development and regulates the amount of toner on the developing carrier by a toner regulating member. As the evaluation cartridge, the toner contained in a commercially available cartridge was taken out, the inside was cleaned by air blow, and a cartridge filled with 260 g of the toner was used. After leaving in a high temperature and high humidity (30.0 ° C, 80.0% RH) environment for 48 hours, use 81.4g / m ² A4 size paper and set the horizontal line pattern to 5% printing rate as 2 sheets / job. Then, a continuous image printing test of 5000 sheets was carried out, and then a solid black image with a printing rate of 100% was output and the image density was measured. Evaluation was performed in a normal temperature and humidity environment (23.0 ° C., 50% RH). The image density was measured by measuring the reflection density of a 5 mm round solid image using an SPI filter with a Macbeth densitometer (Macbeth Co.) which is a reflection densitometer.

  The evaluation criteria for each item are shown below. The evaluation results are shown in Table 3.

<Particle size distribution>
A: Less than 1.10 B: 1.10 or more and less than 1.20 C: 1.20 or more and less than 1.30 D: 1.30 or more

<aspect ratio>
A: Less than 1.100 B: 1.100 or more and less than 1.150 C: 1.150 or more and less than 1.200 D: 1.200 or more

<Fine powder ratio>
A: Less than 5.0% by number B: 5.0% by number or more and less than 10.0% by number C: 10.0% by number or more and less than 15.0% by number D: 15.0% by number or more

<Initial concentration after leaving in a hot and humid environment>
A: 10th reflection density 1.40 or more B: 10th reflection density 1.30 or more and less than 1.40 C: 10th reflection density 1.20 or more and less than 1.30 D: 10th sheet Reflection density less than 1.20

  T1: Granulation tank, T2: Resin solution tank, T3: Solvent recovery tank, B1: Cylinder, P1, P2: Pump, V1, V2: Valve, V3: Pressure adjustment valve

Claims (4)

a) a step of preparing a resin solution by mixing a binder resin, a colorant and an organic solvent capable of dissolving the binder resin;
b) a step of forming droplets of the resin solution by mixing and granulating the resin solution and a hydrophobic dispersion medium containing organic-inorganic composite fine particles as a dispersant;
c) removing the organic solvent contained in the droplets to obtain toner particles;
In a method for producing a toner having
The organic-inorganic composite fine particles are
(1) Hydrophobized,
(2) The number average diameter is 50 nm or more and 500 nm or less,
(3) A structure in which inorganic fine particles are embedded in resin particles and the surface has a convex portion derived from the inorganic fine particles, and the presence rate of the inorganic fine particles on the surface of the organic-inorganic composite fine particles is 20% or more and 70% or less. Oh it is,
The hydrophobic dispersion medium is a high-pressure dispersion medium containing carbon dioxide.
And a method for producing the toner.   2. The toner production method according to claim 1, wherein the number average diameter of the organic-inorganic composite fine particles is 70 nm or more and 400 nm or less.   3. The toner manufacturing method according to claim 1, wherein the inorganic fine particles are present at a surface ratio of 40% or more and 60% or less on the surface of the organic / inorganic composite fine particles.   4. The addition amount of the organic-inorganic composite fine particles with respect to 100 parts by mass of the binder resin is 2.5 parts by mass or more and 25.0 parts by mass or less. Toner manufacturing method.

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