JP2006053292A - Toner manufacturing method, toner manufacturing apparatus and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner excellent in charging characteristics and having a uniform shape and a narrow particle size distribution, and to provide a toner manufacturing method and a toner manufacturing apparatus by which such a toner can be efficiently manufactured in an environmentally friendly way. <P>SOLUTION: The toner manufacturing method uses a dispersion in which a dispersoid containing a resin material is dispersed in a dispersion medium and which contains a dispersant having a function to improve the dispersibility of the dispersoid. The dispersant has a molecular structure with a carbon-carbon unsaturated bond, and after discharging the dispersion as a liquid drop-like discharge, this discharge is ozonized. The dispersion medium consists mainly of water and/or liquid excellent in compatibility with water. The ozonization is carried out by exposing the discharge to an atmosphere containing ozone at a concentration of 0.1-100 ppm. A preferred exposure time of the discharge to the atmosphere is 0.1-30 min. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner manufacturing method, a toner manufacturing apparatus, and a toner.

A number of methods are known as electrophotographic methods. In general, a process (exposure process) of forming an electrical latent image on a photoconductor by various means using a photoconductive substance, The toner image is fixed by a developing process that develops the latent image using toner (resin fine particles), a transfer process that transfers the toner image onto a transfer material such as paper, and heating and pressurization using a fixing roller. Process.
As a method for producing the toner used in such an electrophotographic method, a pulverization method and a polymerization method are used.

  In the pulverization method, a raw material containing a resin as a main component (hereinafter also simply referred to as “resin”) and a colorant is kneaded at a temperature equal to or higher than the softening point of the resin to obtain a kneaded product, and then the kneading. This is a method of cooling and crushing an object. Such a pulverization method is excellent in that the range of selection of raw materials is wide and toner can be produced relatively easily. However, the toner obtained by the pulverization method has the disadvantage that the variation in shape among the particles is large, and the particle size distribution tends to be wide. As a result, variations in charging characteristics, fixing characteristics, etc. among the toner particles become large, and the reliability of the whole toner is lowered.

  In the polymerization method, toner particles are produced by performing a polymerization reaction in a liquid phase or the like using a monomer that is a constituent component of a resin to produce a target resin. In such a polymerization method, usually in a liquid phase containing a dispersant for the purpose of improving the dispersibility of the dispersoid (dispersoid to be toner particles), monodispersing, controlling the molecular weight distribution, etc. The polymerization reaction is carried out. Such a polymerization method is excellent in that the shape of the obtained toner particles can be made to have a relatively high sphericity (geometrically close to a perfect sphere). However, in the conventional polymerization method, it is difficult to obtain a toner having excellent charging characteristics in the finally obtained toner. That is, in the conventional polymerization method, it is difficult to make the absolute value of the charge amount of the toner particles sufficiently large in the finally obtained toner, or the charge characteristics (charge amount) between the toner particles. There was a problem that the variation in the thickness was likely to increase.

  In recent years, a method for producing toner particles by discharging a dispersion containing a raw material for toner production using a so-called inkjet method has been proposed (for example, see Patent Document 1). In such a method, a dispersion added with a dispersant is usually used for the purpose of making the content of the dispersoid in the discharged droplets uniform or enabling the dispersion to be discharged. In other words, when a dispersion containing no dispersant is used, a toner having a uniform shape and size cannot be obtained, and furthermore, the dispersion itself cannot be discharged. When such a method is adopted, although the variation in shape and size among the particles can be made relatively small, it has been difficult to obtain a toner having excellent charging characteristics as in the polymerization method described above.

JP 2004-70303 A

  An object of the present invention is to provide a toner having excellent charging characteristics, a uniform shape, and a small particle size distribution, and a toner production method capable of efficiently producing such a toner, To provide a toner manufacturing apparatus. In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be contained in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and a width of the particle size distribution. It is to provide a small toner.

Such an object is achieved by the present invention described below.
The toner production method of the present invention produces a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and contains a dispersant having a function of improving the dispersibility of the dispersoid. A method,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
Ozone is applied during and / or after the dispersion medium removing step of removing the dispersion medium from the dispersion.

  As a result, it is possible to provide a toner manufacturing method capable of efficiently (highly producing) toner particles having excellent charging characteristics, a uniform shape, and a narrow particle size distribution. In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be contained in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and a width of the particle size distribution. It is possible to provide a production method capable of producing a small toner.

The toner production method of the present invention produces a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and contains a dispersant having a function of improving the dispersibility of the dispersoid. A method,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
After the dispersion is discharged as a droplet-like discharge, ozone is applied to the discharge.

  As a result, it is possible to provide a toner manufacturing method capable of efficiently (highly producing) toner particles having excellent charging characteristics, a uniform shape, and a narrow particle size distribution. In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be contained in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and a width of the particle size distribution. It is possible to provide a production method capable of producing a small toner.

In the toner manufacturing method of the present invention, it is preferable that the discharged material includes a plurality of the dispersoids.
As a result, it is possible to obtain a toner having particularly small variations in shape, size, and the like between particles (between toner particles).
In the toner production method of the present invention, after the dispersion medium removing step of removing the dispersion medium from the dispersion, the ozone is applied in a step of joining a plurality of the dispersoids constituting the ejected matter. Is preferred.
Thereby, the dispersant can be efficiently decomposed with a relatively small amount of ozone.

In the method for producing a toner of the present invention, it is preferable that the ozone is applied to the discharged matter in a dispersion medium removing step of removing the dispersion medium from the dispersion.
As a result, the contact time between the discharged material (dispersion liquid, aggregate from which the dispersion medium has been removed from the dispersion liquid) and ozone can be extended, and ozone can be efficiently used for removal of the dispersant. . In addition, it is possible to effectively prevent degradation and decomposition of the toner constituent material (component to be contained in the toner) in contact with ozone, thereby obtaining a more reliable toner. Can do.

In the method for producing a toner of the present invention, it is preferable that the discharged material is exposed to an atmosphere containing ozone.
Thereby, ozone in a homogeneous state can be more reliably applied to each discharge (aggregate obtained by removing the dispersion medium from the dispersion). As a result, the finally obtained toner has a small variation in characteristics between each particle (between toner particles), and the reliability of the whole toner is improved.

In the toner manufacturing method of the present invention, the ozone concentration in the atmosphere is preferably 0.1 to 100 ppm.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).
In the method for producing a toner of the present invention, the exposure time of the discharged material to the atmosphere is preferably 0.1 to 30 minutes.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).
In the toner manufacturing method of the present invention, it is preferable that the dispersion is intermittently ejected by piezoelectric pulses.
As a result, it is possible to more efficiently obtain a toner having a particularly small variation in shape, size, and the like between particles (between toner particles).

The toner production method of the present invention produces a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and contains a dispersant having a function of improving the dispersibility of the dispersoid. A method,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
It has the process of providing ozone to the said dispersion liquid.

  As a result, it is possible to provide a toner manufacturing method capable of efficiently (highly producing) toner particles having excellent charging characteristics, a uniform shape, and a narrow particle size distribution. In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be contained in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and a width of the particle size distribution. It is possible to provide a production method capable of producing a small toner.

In the toner production method of the present invention, the dispersion preferably contains an anionic dispersant and / or a nonionic dispersant as the dispersant.
Thereby, even if the conditions of the treatment using ozone are relatively mild, the charging characteristics of the finally obtained toner can be more reliably improved.

In the toner manufacturing method of the present invention, the content of the dispersant in the dispersant is preferably 0.001 to 10 wt%.
As a result, the charging characteristics of the toner can be made particularly excellent while the variation in shape, size, etc. between the particles (between toner particles) is made particularly small. Further, the toner productivity can be made particularly high.

In the method for producing a toner of the present invention, it is preferable that the dispersion medium is mainly composed of water and / or a liquid having excellent compatibility with water.
Thereby, the toner can be manufactured by a more environmentally friendly method. Further, for example, the dispersibility of the dispersoid in the dispersion medium can be enhanced, and the dispersoid in the dispersion can have a relatively small particle size and a particularly small variation in size. As a result, it is possible to efficiently manufacture a toner having a particularly small variation in shape and variation in size between particles (between toner particles).

In the method for producing a toner of the present invention, the dispersion preferably contains a charge control agent.
Thereby, the charging characteristics of the toner can be made particularly excellent.
In the toner production method of the present invention, the resin material preferably has a molecular structure that does not have a carbon-carbon unsaturated bond in the molecule.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).

In the toner production method of the present invention, the weight average molecular weight of the dispersant is Mw (d), and the average number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d) [pieces]. ], It is preferable to satisfy the relationship of N (d) / Mw (d) ≧ 0.003.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).

In the toner production method of the present invention, the weight average molecular weight of the resin material is Mw (r), and the average value of the number of carbon-carbon unsaturated bonds present in one molecule of the resin material is N (r) [pieces]. ], It is preferable to satisfy the relationship of N (r) / Mw (r) ≦ 0.02.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).

In the toner production method of the present invention, the weight average molecular weight of the monomer unit of the dispersant is M (d), and the average number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d ) [Number], when the weight average molecular weight of the resin material is Mw (r), and the average number of carbon-carbon unsaturated bonds present in one molecule of the resin material is N (r) [number] [N (r) / Mw (r)] / [N (d) / Mw (d)] ≦ 5 is preferably satisfied.
Thereby, it is possible to decompose the dispersant more efficiently while more reliably preventing the deterioration of the constituent components of the toner (particularly, the resin material as the binder resin).

The toner manufacturing apparatus of the present invention is used in the manufacturing method of the present invention.
As a result, it is possible to provide a toner manufacturing apparatus capable of efficiently (with good productivity) manufacturing toner particles having excellent charging characteristics, a uniform shape, and a narrow particle size distribution. In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be included in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and a width of the particle size distribution. It is possible to provide a manufacturing apparatus capable of manufacturing a small toner.

The toner manufacturing apparatus of the present invention includes a discharge unit that discharges the dispersion liquid,
It is preferable that the apparatus includes an ozone applying unit that applies ozone to the dispersion liquid discharged from the discharge unit.
As a result, the contact time between the discharged material (dispersion liquid, aggregate from which the dispersion medium has been removed from the dispersion liquid) and ozone can be extended, and ozone can be efficiently used for removal of the dispersant. . In addition, it is possible to effectively prevent degradation and decomposition of the toner constituent material (component to be contained in the toner) in contact with ozone, thereby obtaining a more reliable toner. Can do.
The toner manufacturing apparatus of the present invention includes an ozone applying unit that removes at least a part of the dispersion medium from the dispersion and applies ozone to a granular dispersion medium removal product composed of a plurality of the dispersoids. Preferably it is.
Thereby, the dispersant can be efficiently decomposed with a relatively small amount of ozone.

In the toner manufacturing apparatus of the present invention, it is preferable that a region for joining a plurality of dispersoids constituting the dispersion medium removal product is provided.
Thereby, the mechanical strength of the toner (toner particles) can be made particularly excellent. Further, by applying ozone in the bonding region, the reactivity between ozone and the dispersant can be further increased, and the dispersant can be efficiently decomposed with a smaller amount of ozone.

The toner of the present invention is manufactured using the method of the present invention.
As a result, it is possible to provide a toner having excellent charging characteristics, a uniform shape, and a narrow particle size distribution.
The toner of the present invention is manufactured using the apparatus of the present invention.
As a result, it is possible to provide a toner having excellent charging characteristics, a uniform shape, and a narrow particle size distribution.

<< Outline of the Invention >>
A number of methods are known as electrophotographic methods. In general, a process (exposure process) of forming an electrical latent image on a photoconductor by various means using a photoconductive substance, The toner image is fixed by a developing process that develops the latent image using toner (resin fine particles), a transfer process that transfers the toner image onto a transfer material such as paper, and heating and pressurization using a fixing roller. Process.

As a method for producing the toner used in such an electrophotographic method, a pulverization method and a polymerization method are used.
In the pulverization method, a raw material containing a resin as a main component (hereinafter also simply referred to as “resin”) and a colorant is kneaded at a temperature equal to or higher than the softening point of the resin to obtain a kneaded product, and then the kneading. This is a method of cooling and crushing an object. Such a pulverization method is excellent in that the range of selection of raw materials is wide and toner can be produced relatively easily. However, the toner obtained by the pulverization method has the disadvantages that the shape variation among the particles is large and the particle size distribution tends to be wide. As a result, variations in charging characteristics, fixing characteristics and the like among the toner particles become large, and the reliability of the whole toner is lowered.

  In the polymerization method, toner particles are produced by performing a polymerization reaction in a liquid phase or the like using a monomer that is a constituent component of a resin to produce a target resin. In such a polymerization method, the polymerization reaction is usually performed in a liquid phase containing a dispersant for the purpose of improving the dispersibility of the dispersoid (the dispersoid to be the toner particles). Such a polymerization method is excellent in that the shape of the obtained toner particles can be made to have a relatively high sphericity (geometrically close to a perfect sphere). However, in the conventional polymerization method, it is difficult to obtain a toner having excellent charging characteristics in the finally obtained toner. That is, in the conventional polymerization method, it is difficult to make the absolute value of the charge amount of the toner particles sufficiently large in the finally obtained toner, or the charge characteristics (charge amount) between the toner particles. There was a problem that the variation in the thickness was likely to increase.

  In recent years, a method for producing toner particles by using a so-called ink jet method to eject a dispersion containing a raw material for toner production has been proposed. In such a method, a dispersion added with a dispersant is usually used for the purpose of making the content of the dispersoid in the discharged droplets uniform or enabling the dispersion to be discharged. In other words, when a dispersion containing no dispersant is used, a toner having a uniform shape and size cannot be obtained, and furthermore, the dispersion itself cannot be discharged. When such a method (inkjet method) is adopted, the variation in shape and size among the particles can be made relatively small, but it is difficult to obtain a toner having excellent charging characteristics as in the polymerization method described above. Met.

  As described above, when a method using a dispersion liquid is adopted, it is difficult to obtain a toner having excellent charging characteristics, although it is possible to reduce variation in shape between particles (between toner particles). It was. Conventionally, when a method using a dispersion liquid is adopted, the obtained toner is inferior in environmental characteristics (water resistance, storage stability) and stored in a cartridge (especially under high humidity conditions). In other words, there is a problem that aggregation between toner particles occurs and so-called lumps are easily generated. Therefore, the present inventor has conducted intensive research for the purpose of solving the above problems. As a result, the present inventor has found that the dispersing agent contained in the dispersion remains in the toner, thereby adversely affecting the charging characteristics of the toner, and further includes a carbon-carbon unsaturated bond as the dispersing agent. It has been found that the toner having excellent characteristics can be obtained by selectively removing the dispersant by using a material having a molecular structure and using ozone.

Hereinafter, preferred embodiments of a toner production method, a toner production apparatus, and a toner according to the present invention will be described in detail with reference to the accompanying drawings.
<< First Embodiment >>
FIG. 1 is a longitudinal sectional view schematically showing a first embodiment of a toner manufacturing apparatus used for manufacturing the toner of the present invention, and FIG. 2 is an enlarged sectional view in the vicinity of the head portion of the toner manufacturing apparatus shown in FIG. is there.

[Dispersion]
First, the dispersion used in the present invention will be described. The toner of the present invention is produced using a dispersion containing a dispersant. Examples of the dispersion include suspensions (suspensions) and emulsions (emulsions, emulsions, and emulsions). In this specification, “suspension” refers to a dispersion (including a suspended colloid) in which a solid (solid) dispersoid (suspended particle) is dispersed in a liquid dispersion medium. The term “emulsified liquid (emulsion, emulsion, milky liquid)” refers to a dispersion in which a liquid dispersoid (dispersed particles) is dispersed in a liquid dispersion medium. In the dispersion liquid, a solid dispersoid and a liquid dispersoid may coexist. In such a case, among the dispersoids in the dispersion, those in which the proportion of the solid dispersoid is larger than the proportion of the liquid dispersoid is called a suspension, and the proportion of the liquid dispersoid is solid. What is larger than the proportion of the dispersoid in the form of a powder is called an emulsion. In particular, it is preferable that the dispersion used in the present invention has been deaerated. The deaeration process will be described in detail later.
The dispersion 6 has a configuration in which a dispersoid (dispersed phase) 61 is finely dispersed in a dispersion medium 62. The dispersion 6 contains a dispersant having a function of improving the dispersibility of the dispersoid 61.

<Dispersion medium>
The dispersion medium 62 may be any material as long as the dispersoid 61 described below can be dispersed, but is mainly a material generally used as a solvent (hereinafter also referred to as “solvent material”). It is preferred that it is constructed.
Examples of such materials include inorganic solvents such as water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, Ketone solvents such as 3-heptanone and 4-heptanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2- Alcohol solvents such as pentanol, n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, diethyl ether, dipropyl ether Ether solvents such as diisopropyl ether, dibutyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), 2-methoxyethanol Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, methylcyclohexane, octane, didecane, methylcyclohexene, isoprene, toluene, xylene, benzene, ethylbenzene , Aromatic hydrocarbon solvents such as naphthalene, pyridine, pyrazine, furan, pyrrole, thiophene, 2-methylpyridine, 3-methylpyridine, 4-methyl Aromatic heterocyclic compound solvents such as pyridine and furfuryl alcohol, amide solvents such as N, N-dimethylformamide (DMF) and N, N-dimethylacetamide (DMA), dichloromethane, chloroform, 1,2-dichloroethane, Halogenated solvents such as trichloroethylene and chlorobenzene, acetylacetone, ethyl acetate, methyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, isobutyl formate, ethyl acrylate, methacrylic acid Ester solvents such as methyl acid, ethyl benzoate, amine solvents such as trimethylamine, hexylamine, triethylamine, aniline, nitrile solvents such as acrylonitrile, acetonitrile, nitromethane, Examples include nitro solvents such as nitroethane, organic solvents such as aldehyde solvents such as acetaldehyde, propionaldehyde, butyraldehyde, pentanal, and acrylic aldehyde. A mixture of one or more selected from these is used. be able to.

  Among the above materials, the dispersion medium 62 is mainly composed of water and / or a liquid having excellent compatibility with water (for example, a liquid having a solubility in 100 g of water at 25 ° C. of 30 g or more). preferable. Thereby, for example, the dispersibility of the dispersoid 61 in the dispersion medium 62 can be improved, and the dispersoid 61 in the dispersion liquid 6 has a relatively small particle size and small variation in size. be able to. As a result, the finally obtained toner (toner particles) has a small variation in size and shape among the particles, and has a large circularity. In particular, when the dispersion medium 62 is composed of water, for example, in the toner manufacturing process, the organic solvent can be substantially prevented from volatilizing. As a result, the toner can be produced by a method that hardly causes adverse effects on the environment, that is, an environmentally friendly method. Further, when the dispersion medium 62 is mainly composed of water and / or a liquid having excellent compatibility with water, a dispersant as described in detail later in the dispersion liquid 6 is efficiently applied to the vicinity of the surface of the dispersoid 61. It can be well distributed. As a result, by applying ozone as described in detail later, the dispersant can be selectively decomposed and removed while sufficiently preventing degradation and deterioration of the binder resin (resin material) that is a constituent material of the toner. . As a result, the finally obtained toner has particularly excellent characteristics.

  When a mixture of a plurality of components is used as the constituent material of the dispersion medium 62, the constituent material of the dispersion medium is an azeotrope (lowest boiling point azeotrope) between at least two components constituting the mixture. It is preferable to use one that can form As a result, it is possible to efficiently remove the dispersion medium 62 in the conveyance unit of the toner manufacturing apparatus described later. In addition, it becomes possible to remove the dispersion medium 62 at a relatively low temperature in a transport unit of a toner manufacturing apparatus described later, and it is possible to more effectively prevent deterioration of the characteristics of the finally obtained toner (toner particles). For example, liquids that can form an azeotrope with water include carbon disulfide, carbon tetrachloride, methyl ethyl ketone (MEK), acetone, cyclohexanone, 3-heptanone, 4-heptanone, ethanol, n-propanol, Isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, dipropyl ether, dibutyl ether, 1,4-dioxane, anisole, 2-methoxyethanol, hexane, heptane, cyclohexane, methylcyclohexane, octane, dideca , Methylcyclohexene, isoprene, toluene, benzene, ethylbenzene, naphthalene, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, furfuryl alcohol, chloroform, 1,2-dichloroethane, trichloroethylene, chlorobenzene, acetylacetone, acetic acid Ethyl acetate, methyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, isobutyl formate, ethyl acrylate, methyl methacrylate, ethyl benzoate, trimethylamine, hexylamine, triethylamine Aniline, acrylonitrile, acetonitrile, nitromethane, nitroethane, acrylic aldehyde and the like.

Further, the boiling point of the dispersion medium 62 is not particularly limited, but is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 35 to 130 ° C. As described above, when the boiling point of the dispersion medium 62 is relatively low, the dispersion medium 62 can be removed relatively easily in the conveyance unit of the toner manufacturing apparatus described later. Further, by using such a material as the dispersion medium 62, the residual amount of the dispersion medium 62 in the finally obtained toner particles can be made particularly small. As a result, the reliability as a toner is further increased.
The dispersion medium 62 may contain components other than the materials described above. For example, in the dispersion medium 62, various materials such as materials exemplified later as constituents of the dispersoid 61, inorganic fine powders such as silica, titanium oxide, and iron oxide, organic fine powders such as fatty acids and fatty acid metal salts, etc. Additives and the like may be included.

<Dispersed quality>
The dispersoid 61 is usually made of a material containing at least a resin as a main component or a precursor thereof (hereinafter collectively referred to as “resin material”). Examples of the resin precursor include a monomer, a dimer, an oligomer, and a prepolymer of the resin.

Hereinafter, the constituent material of the dispersoid 61 will be described.
1. Resin (binder resin)
Examples of the resin (binder resin) include (meth) acrylic resin, polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, and styrene-butadiene copolymer. Styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester-methacrylic acid Styrene resin such as acid ester copolymer, styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, styrene-vinyl methyl ether copolymer, etc. Homopolymer or copolymer, poly Ester resin, epoxy resin, urethane modified epoxy resin, silicone modified epoxy resin, vinyl chloride resin, rosin modified maleic acid resin, phenyl resin, polyethylene, polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl acrylate A polymer, a xylene resin, a polyvinyl butyral resin, a terpene resin, a phenol resin, an aliphatic or alicyclic hydrocarbon resin, and the like can be given, and one or more of these can be used in combination. In addition, when a toner is produced by polymerizing a raw material in the dispersoid 61 in a transport unit of a toner production apparatus, which will be described later, usually a precursor of the above resin (for example, a monomer, a dimer, an oligomer, a pre-polymer). Polymer).

  Even if the resin material constituting the dispersoid 61 has a molecular structure that does not include a carbon-carbon unsaturated bond, or a carbon-carbon unsaturated bond that will be described in detail later, It is preferable that the ratio of carbon-carbon unsaturated bonds (the number of carbon-carbon unsaturated bonds present in one molecule) is relatively small. Thereby, in the ozone provision process mentioned later, a dispersing agent can be decomposed | disassembled more efficiently, preventing deterioration of a resin material more reliably.

More specifically, when the weight average molecular weight of the resin material is Mw (r) and the average number of carbon-carbon unsaturated bonds existing in one molecule of the resin material is N (r) [pieces], It is preferable to satisfy the relationship of N (r) / Mw (r) ≦ 0.02, more preferable to satisfy the relationship of N (r) / Mw (r) ≦ 0.015, and N (r) / More preferably, the relationship of Mw (r) ≦ 0.01 is satisfied. By satisfying such a relationship, it is possible to decompose the dispersant more efficiently while preventing the deterioration of the resin material more reliably in the ozone application step described later. In addition, when the resin material is composed of a plurality of types of materials (components), the weight average molecular weight Mw (r) of the resin material, the number of carbon-carbon unsaturated bonds present in one molecule of the resin material As the average value N (r), values obtained as weighted average values based on the weights of these components can be employed.
Although content of the resin material in the dispersoid 61 is not specifically limited, It is preferable that it is 2-98 wt%, and it is more preferable that it is 5-95 wt%.

  Moreover, it is preferable that the glass transition point of the resin material which comprises the dispersoid 61 is 50-70 degreeC. As a result, it is possible to efficiently obtain a toner with little deterioration of the constituent material, excellent shape and size uniformity, and excellent mechanical strength. When the resin material constituting the dispersoid 61 is composed of a plurality of types of resin materials (resin components), the glass transition point of the resin material is obtained as a weight-based weighted average value of each component. Values can be adopted.

  The melting point of the resin material constituting the dispersoid 61 is preferably 90 to 150 ° C. Thereby, the joining process mentioned later can be performed efficiently. In addition, when the resin material which comprises the dispersoid 61 is comprised by multiple types of resin material (resin component), the value calculated | required as a weighted average value of the weight reference | standard of these each component as melting | fusing point of a resin material Can be adopted.

2. Solvent The dispersoid 61 may contain a solvent that dissolves at least a part of its components. Thereby, for example, the fluidity of the dispersoid 61 in the dispersion liquid 6 can be improved, and the dispersoid 61 in the dispersion liquid 6 has a relatively small particle size and small variation in size. be able to. As a result, the finally obtained toner can have a small variation in size and shape between particles (between toner particles) and a relatively large circularity.

Any solvent can be used as long as it dissolves at least a part of the components constituting the dispersoid 61, but it can be easily removed by a transport unit of a toner manufacturing apparatus as described later ( For example, it is preferable that the boiling point is 150 ° C. or less.
The solvent is preferably a solvent having low compatibility with the dispersion medium 62 described above (for example, a solvent having a solubility in 100 g of the dispersion medium at 25 ° C. of 30 g or less). Thereby, the dispersoid 61 can be finely dispersed in the dispersion 6 in a stable state.
Moreover, the composition of the solvent can be appropriately selected according to, for example, the composition of the resin and the colorant described above, the composition of the dispersion medium, and the like.

  Examples of the solvent include inorganic solvents such as water, carbon disulfide, and carbon tetrachloride, methyl ethyl ketone (MEK), acetone, diethyl ketone, methyl isobutyl ketone (MIBK), methyl isopropyl ketone (MIPK), cyclohexanone, and 3-heptanone. , Ketone solvents such as 4-heptanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, t-butanol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, Alcohol solvents such as n-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-methoxyethanol, allyl alcohol, furfuryl alcohol, phenol, diethyl ether, dipropyl ether, diisopropyl Ether solvents such as pyr ether, dibutyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), 2-methoxyethanol Cellosolve solvents such as methyl cellosolve, ethyl cellosolve, phenyl cellosolve, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, cyclohexane, methylcyclohexane, octane, didecane, methylcyclohexene, isoprene, toluene, xylene, benzene, ethylbenzene , Aromatic hydrocarbon solvents such as naphthalene, pyridine, pyrazine, furan, pyrrole, thiophene, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine Aromatic heterocyclic compound solvents such as furfuryl alcohol, amide solvents such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA), dichloromethane, chloroform, 1,2-dichloroethane, trichlorethylene, Halogenated solvents such as chlorobenzene, acetylacetone, ethyl acetate, methyl acetate, isopropyl acetate, isobutyl acetate, isopentyl acetate, ethyl chloroacetate, butyl chloroacetate, isobutyl chloroacetate, ethyl formate, isobutyl formate, ethyl acrylate, methyl methacrylate Ester solvents such as ethyl benzoate, amine solvents such as trimethylamine, hexylamine, triethylamine and aniline, nitrile solvents such as acrylonitrile and acetonitrile, nitromethane, nitroethane Organic solvents such as nitro solvents such as aldehyde, aldehyde solvents such as acetaldehyde, propionaldehyde, butyraldehyde, pentanal, acrylic aldehyde, etc. are used, and one or a mixture of two or more selected from these is used. be able to. Among these, those containing an organic solvent are preferred, and ether solvents, cellosolve solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, aromatic heterocyclic compounds solvents, amide solvents, halogen compound solvents. More preferably, the solvent contains one or more selected from a solvent, an ester solvent, a nitrile solvent, a nitro solvent, and an aldehyde solvent. By using such a solvent, the above-described components can be dispersed sufficiently uniformly in the dispersoid 61 relatively easily.

  Further, in the dispersion 6 (particularly in the dispersoid 61), a colorant is usually contained. Examples of the colorant that can be used include pigments and dyes. Examples of such pigments and dyes include carbon black, spirit black, lamp black (CI No. 77266), magnetite, titanium black, chrome lead, cadmium yellow, mineral fast yellow, navel yellow, and naphthol yellow S. , Hansa Yellow G, Permanent Yellow NCG, Chrome Yellow, Benzidine Yellow, Quinoline Yellow, Tartrazine Lake, Red Mouth Lead, Molybdenum Orange, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Cadmium Red, Permanent Red 4R, Watching Red Calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, methyl violet lake, bitumen, cobalt blue, al Reblue Lake, Victoria Blue Lake, First Sky Blue, Indanthrene Blue BC, Ultramarine, Aniline Blue, Phthalocyanine Blue, Calco Oil Blue, Chrome Green, Chrome Oxide, Pigment Green B, Malachite Green Lake, Phthalocyanine Green, Final Yellow Green G, Rhodamine 6G, quinacridone, rose bengal (C.I. No. 45432), C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 184, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 5: 1, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 162, nigrosine dye (CI No. 50415B), metal complex dye, silica, aluminum oxide, magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, Examples thereof include metal oxides such as magnesium oxide, and magnetic materials containing magnetic metals such as Fe, Co, and Ni, and one or more of these can be used in combination. Such a colorant is usually contained in the dispersoid 61 in the dispersion liquid 6.

  The content of the colorant in the dispersoid 61 is not particularly limited, but is preferably 0.1 to 10 wt%, and more preferably 0.3 to 3.0 wt%. If the content of the colorant is less than the lower limit, it may be difficult to form a visible image having a sufficient density depending on the type of the colorant. On the other hand, when the content of the colorant exceeds the upper limit, the fixing characteristics and charging characteristics of the finally obtained toner may be deteriorated.

  Further, the dispersion 6 may contain wax. The wax is usually used for the purpose of improving releasability. Examples of such wax include plant waxes such as candelilla wax, carnauba wax, rice wax, cotton wax, and wood wax, animal waxes such as beeswax and lanolin, montan wax, ozokerite, and ceresin. Mineral waxes such as mineral waxes, paraffin waxes, microwaxes, microcrystalline waxes, petroleum waxes such as petrolatum waxes, Fischer-Tropsch waxes, polyethylene waxes (polyethylene resins), polypropylene waxes (polypropylene resins) ), Synthetic hydrocarbon waxes such as oxidized polyethylene wax and oxidized polypropylene wax, 12-hydroxy stearamide, stearamide, phthalic anhydride, chlorinated hydrocarbon Fatty acid amides, esters, ketones, synthetic wax wax such as ether and the like, can be used singly or in combination of two or more of them. Further, as the wax, a crystalline polymer resin having a lower molecular weight may be used. For example, a homopolymer or copolymer of polyacrylate such as poly n-stearyl methacrylate and poly n-lauryl methacrylate (for example, It is also possible to use a crystalline polymer having a long alkyl group in the side chain, such as an n-stearyl acrylate-ethyl methacrylate copolymer).

The wax content in the dispersion 6 is not particularly limited, but is preferably 1.0 wt% or less, and more preferably 0.5 wt% or less. If the content of the wax is too large, the wax is liberated and coarsened in the finally obtained toner particles, and the toner seeps into the toner particle surface and the transfer efficiency of the toner tends to decrease. Indicates.
The softening point of the wax is not particularly limited, but is preferably 50 to 180 ° C, and more preferably 60 to 160 ° C.

  Further, the dispersion liquid 6 contains a dispersant. Thus, the dispersibility of the dispersoid 61 in a dispersion liquid improves because the dispersion liquid 6 contains a dispersing agent. As a result, a toner with small variations in size and shape between each particle (between toner particles) can be obtained. In the present specification, “dispersant” refers to a substance having a function of improving the dispersibility of a dispersoid in a dispersion, and includes a concept including an emulsifier, a dispersion aid and the like in addition to a narrowly defined dispersant. It is.

  In particular, the present invention is characterized in that a dispersant having a molecular structure having a carbon-carbon unsaturated bond is used. Such a dispersant has a high reactivity with ozone, and is decomposed and removed in preference to the constituent material of the toner (component to be contained in the toner) in the ozone application step described in detail later. In other words, by using such a dispersant, it is possible to selectively decompose and remove the dispersant while effectively preventing the constituent materials of the toner (components to be contained in the toner) from being decomposed and degraded by ozone. be able to. As a result, toner particles having excellent charging characteristics, a uniform shape, and a narrow particle size distribution can be produced efficiently (with good productivity). In particular, the characteristics (for example, charging characteristics, fixing properties, etc.) of the constituent materials of the toner (components to be contained in the toner) are sufficiently exhibited by an environmentally friendly method, have a uniform shape, and have a particle size distribution. A toner having a small width can be produced.

  In the present invention (this specification), the carbon-carbon unsaturated bond refers to a π-electron that contributes to the bond in the adjacent carbon-carbon bond. Examples of such a substance having a carbon-carbon unsaturated bond include a resonance hybrid having a plurality of resonance structures (limit structural formula, contributing structure) in addition to those having independent double bonds and triple bonds. Etc. are also included. That is, in the present invention, the carbon-carbon unsaturated bond is not limited to an integer having a bond order of 2 or 3, but also includes a bond order other than an integer having a bond order of 3/2 or 4/3. It is. Examples of the partial structure having a plurality of resonance structures (limit structural formula, contributing structure) (including a carbon-carbon unsaturated bond whose bond order is other than an integer) include various aromatic rings, conjugated dienes, and the like. Is mentioned.

  Further, when the weight average molecular weight of the dispersant is Mw (d) and the average value of the number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d) [number], N (d) /Mw(d)≧0.003 is preferably satisfied, N (d) / Mw (d) ≧ 0.004 is more preferable, and N (d) / Mw (d) It is more preferable that the relationship of ≧ 0.0045 is satisfied. By satisfying such a relationship, the dispersant can be decomposed more efficiently in the ozone application step described later while more reliably preventing the deterioration of the constituent components of the toner (particularly the resin material as the binder resin). be able to. In the case where the dispersant is composed of a plurality of types of materials (components), the weight average molecular weight Mw (d) of the dispersant, the number of carbon-carbon unsaturated bonds present in one molecule of the dispersant. As the average value N (d), values obtained as weighted average values based on the weights of these components can be employed.

The weight average molecular weight of the dispersant is Mw (d), the average number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d) [pieces], and the weight average molecular weight of the resin material is Mw (r), where the average value of the number of carbon-carbon unsaturated bonds present in one molecule of the resin material is N (r) [number], [N (r) / Mw (r)] / [ It is preferable to satisfy the relationship of N (d) / Mw (d)] ≦ 5, and a relationship of [N (r) / Mw (r)] / [N (d) / Mw (d)] ≦ 3.3 Is more preferable, and it is further preferable that the relationship [N (r) / Mw (r)] / [N (d) / Mw (d)] ≦ 2 is satisfied. By satisfying such a relationship, the dispersant can be decomposed more efficiently in the ozone application step described later while more reliably preventing the deterioration of the constituent components of the toner (particularly the resin material as the binder resin). be able to.
In addition, when the dispersing agent has a plurality of resonance structures (limit structural formula, contributing structure), the number of carbon-carbon unsaturated bonds is a plurality of resonance structures (limit structural formula, contributing structure). Of these, the number of carbon-carbon unsaturated bonds in the resonance structure having the largest number of carbon-carbon unsaturated bonds present can be employed.

The dispersant used in the present invention may be any as long as it has a molecular structure having a carbon-carbon unsaturated bond. For example, nonionic (nonionic) dispersants, anionic dispersants , Cationic dispersants, amphoteric dispersants and the like.
Examples of nonionic (nonionic) dispersants include ether dispersants, ester dispersants, ether ester dispersants, nitrogen-containing dispersants, and more specifically, acrylic esters, And methacrylic acid esters.

  Examples of the anionic dispersant include various rosins, various carboxylates, various sulfate esters, various sulfonates, various phosphate esters, and more specifically, gum rosin, polymerized rosin, and heterogeneous. Rosin, maleated rosin, fumarized rosin, maleated rosin pentaester, maleated rosin glycerin ester, tristearate (for example, metal salt such as aluminum salt), distearate (for example, aluminum salt, barium salt) Metal salts such as cobalt salts, manganese salts, lead salts, zinc salts, etc.), octanoate salts (such as aluminum salts, calcium salts, cobalt salts, etc.) ), Oleates (eg, metal salts such as calcium salts, cobalt salts, etc.), naphthenates (eg, calcium sulfate) Salt, cobalt salt, manganese salt, lead salt, zinc salt, etc.), resinate (eg, calcium salt, cobalt salt, manganese lead salt, zinc salt etc.), dodecylbenzenesulfonate (For example, sodium salt), alkyl sulfonate, polystyrene sulfonate (for example, metal salt such as sodium salt), alkyl diphenyl ether disulfonate (for example, metal salt such as sodium salt) and the like.

Examples of the cationic dispersant include various ammonium salts such as primary ammonium salt, secondary ammonium salt, tertiary ammonium salt, and quaternary ammonium salt, and more specifically, (mono) alkylamine salt. , Dialkylamine salts, trialkylamine salts, tetraalkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolinium salts, and the like.
Examples of the amphoteric dispersant include various betaines such as carboxybetaine and sulfobetaine, various aminocarboxylic acids, and various phosphate ester salts.

In particular, when an anionic dispersant is used among the above, the treatment conditions using ozone as described in detail later are relatively mild (for example, ozone is applied when the amount of ozone applied is relatively small. Even when the density of the toner is relatively low, the charging characteristics of the finally obtained toner can be more reliably improved.
Moreover, when the thing containing a cationic dispersing agent is used as a dispersing agent, the effect by this invention can be exhibited notably. That is, as the toner, a negatively charged toner is usually widely used. However, when a cationic dispersant is used in the production of such a toner, the content of the cationic dispersant in the final toner Even if the amount is relatively small, the adverse effect on the charging characteristics of the toner is significant. Therefore, in the conventional method in which the dispersant is not removed (method using the dispersion liquid), the negative effect of the cationic dispersant appears as remarkable, but in the present invention, as described in detail later, the dispersion liquid Since the dispersant contained therein can be efficiently removed in the toner production process, the occurrence of the above-described problems can be sufficiently prevented even when a cationic dispersant is used. .
Further, when a nonionic dispersant containing a nonionic dispersant is used as a dispersant, the treatment conditions using ozone as described in detail later are relatively mild (for example, ozone is applied when the amount of ozone applied is relatively small. Even when the density of the toner is relatively low, the charging characteristics of the finally obtained toner can be more reliably improved.

  The content of the dispersant in the dispersion liquid 6 is not particularly limited, but is preferably 0.001 to 10 wt%, more preferably 0.005 to 5 wt%, and 0.01 to 3 wt%. Is more preferable. When the content of the dispersant is within the above range, the dispersibility of the dispersoid 61 in the dispersion 6 is sufficiently excellent, and the dispersant is substantially contained in the finally obtained toner. It does not remain, or the dispersant content (residual amount) can be made sufficiently small. As a result, in the finally obtained toner, the charging characteristics of the toner can be made particularly excellent while the variation in shape, size and the like between the particles (between toner particles) is made particularly small. Further, the toner productivity can be made particularly high.

Further, the dispersion liquid 6 preferably contains a charge control agent. Thereby, the charging characteristics of the finally obtained toner can be made particularly excellent. In addition, in the conventional toner production method using a dispersion, even if a dispersion containing a charge control agent is used, the function of the charge control agent cannot be sufficiently exhibited. This is presumably because the dispersant contained in the dispersion is unevenly distributed over the entire surface of the toner particles. On the other hand, in the present invention, since the dispersant can be effectively prevented from remaining in the final toner, the function of the charge control agent can be exhibited more effectively.
Examples of the charge control agent include a metal salt of benzoic acid, a metal salt of salicylic acid, a metal salt of alkyl salicylic acid, a metal salt of catechol, a metal-containing bisazo dye, a nigrosine dye, a tetraphenylborate derivative, a quaternary ammonium salt, Examples thereof include alkyl pyridinium salts, chlorinated polyesters, and nitrohumic acid.

Further, the dispersion 6 may contain components other than these. Examples of such a component include magnetic powder.
Examples of the magnetic powder include magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and other metal oxides such as Fe, Co, and Ni. The thing comprised with the magnetic material containing a magnetic metal etc. are mentioned.

In addition to the above materials, for example, zinc stearate, zinc oxide, cerium oxide or the like may be added to the dispersion liquid 6.
In addition, components other than the dispersoid 61 may be dispersed in the dispersion 6 as insoluble matters. For example, in the dispersion 6, inorganic fine powders such as silica, titanium oxide, and iron oxide, organic fine powders such as fatty acids and fatty acid metal salts, and the like may be dispersed.

In the dispersion 6, the dispersoid 61 is finely dispersed in the dispersion medium 62.
Although the average particle diameter of the dispersoid 61 in the dispersion liquid 6 is not specifically limited, It is preferable that it is 0.05-1.0 micrometer, and it is more preferable that it is 0.1-0.8 micrometer. When the average particle size of the dispersoid 61 is in such a range, the finally obtained toner particles have a sufficiently high circularity and excellent properties and uniformity in shape among the particles. Become.

  Although content of the dispersoid 61 in the dispersion liquid 6 is not specifically limited, It is preferable that it is 1-99 wt%, and it is more preferable that it is 5-95 wt%. When the content of the dispersoid 61 is less than the lower limit, the circularity of the finally obtained toner particles tends to decrease. On the other hand, when the content of the dispersoid 61 exceeds the upper limit, depending on the composition of the dispersion medium 62 and the like, the viscosity of the dispersion 6 increases, and the shape and size of the finally obtained toner (toner particles) It shows a tendency for variation to increase.

In the dispersion 6, the dispersoid 61 may be in a solid form, in a liquid form, or may coexist. That is, the dispersion 6 may be a suspension or an emulsion.
When the dispersoid 61 is liquid (for example, in a solution state or a molten state), the average particle diameter of the dispersoid 61 finely dispersed in the dispersion medium 62 is relatively easily set to a value in the above range. can do. In addition, when the dispersoid 61 is liquid, variation in shape and size among the dispersoids 61 can be made particularly small, so that the finally obtained toner is between the toner particles. Variations in the shape and size are particularly small.

Further, when the dispersoid 61 is solid, unnecessary components such as a solvent can be effectively prevented from remaining in the finally obtained toner. As a result, the reliability of the toner is particularly excellent. When the dispersoid 61 is solid, that is, when the dispersion 6 is a suspension, for example, the suspension as the dispersion 6 is prepared via an emulsion. There may be. Thereby, the advantage in the case where the dispersoid 61 is in a liquid state is also effectively exhibited while sufficiently exhibiting the advantage in the case where the dispersoid 61 is in a solid state as described above.
Further, the dispersoid 61 dispersed in the dispersion medium 62 may have, for example, substantially the same composition among the particles or may have different compositions. For example, the dispersion 6 may include, as the dispersoid 61, one mainly composed of a resin material and one mainly composed of wax.

  Further, when the dispersion 6 is an emulsion (emulsion), the dispersion 6 is an O / W emulsion, that is, a liquid having a low solubility in water in the aqueous dispersion medium 62. The dispersoid 61 is preferably dispersed. As a result, it is possible to stably manufacture a toner having a small variation in shape and size between particles (between toner particles). In addition, by using an aqueous liquid for the dispersion medium 62, the volatilization amount of the organic solvent in the conveying unit of the toner manufacturing apparatus as described later can be reduced, or the organic solvent can be substantially not volatilized. As a result, the toner can be manufactured by a method that hardly causes adverse effects on the environment.

  Further, when the average particle size of the dispersoid 61 in the dispersion 6 is Dm [μm] and the average particle size of the toner particles is Dt [μm], the relationship of 0.005 ≦ Dm / Dt ≦ 0.5 is satisfied. It is preferable to satisfy the relationship of 0.01 ≦ Dm / Dt ≦ 0.2. By satisfying such a relationship, a toner having a particularly small variation in shape and size between each particle (between toner particles) can be obtained.

The dispersion 6 as described above can be prepared using, for example, the following method (first method).
First, an aqueous solution containing water or a liquid excellent in compatibility with water (water-soluble liquid) and a dispersant is prepared.
On the other hand, a resin liquid containing a resin material as a main component of the toner is prepared. For the preparation of the resin liquid, for example, the above-described solvent may be used in addition to the resin material. The resin liquid may be a molten liquid obtained by heating a resin material.

  Next, the dispersion liquid 6 in which the dispersoid 61 containing the resin material is dispersed in the aqueous dispersion medium 62 is obtained by adding the resin liquid while gradually dropping into the stirred aqueous solution. can get. By preparing the dispersion 6 by such a method, the circularity of the dispersoid 61 in the dispersion 6 can be further increased. As a result, the finally obtained toner particles have a particularly high degree of circularity, and the variation in shape between the particles (between toner particles) is particularly small. In addition, when dripping a resin liquid, you may heat an aqueous solution and / or a resin liquid. In addition, when a solvent is used for the preparation of the resin liquid, for example, after the dropwise addition as described above, the obtained dispersion liquid 6 is heated or placed in a reduced-pressure atmosphere or the like in the dispersoid 61. You may remove at least one part of the solvent contained. For example, the dispersion 6 can be obtained as a suspension by removing most of the solvent contained in the dispersoid 61. When such a method is adopted, the solvent can be easily and reliably recovered. As a result, the toner can be manufactured by a method that hardly causes adverse effects on the environment.

As mentioned above, although the example of the preparation method of the dispersion liquid 6 was demonstrated, the dispersion liquid is not limited to what was prepared by such a method. For example, the dispersion liquid 6 can also be prepared by the following method (second method).
First, an aqueous solution containing water or a liquid excellent in compatibility with water and a dispersant is prepared.
On the other hand, a powdery or granular material containing a resin material is prepared.
Next, a dispersion liquid in which the dispersoid 61 containing the resin material is dispersed in the aqueous dispersion medium 62 by gradually adding the powdery or granular material into the stirred aqueous solution. 6 is obtained. When the dispersion liquid 6 is prepared by such a method, the organic solvent can be substantially prevented from volatilizing in the transport section of the toner manufacturing apparatus as described later. As a result, the toner can be manufactured by a method that hardly causes adverse effects on the environment. In addition, when adding the said material, you may heat an aqueous solution, for example.

The dispersion 6 can also be prepared by the following method (third method).
First, a resin dispersion in which at least a resin material is dispersed and a colorant dispersion in which at least a colorant is dispersed are prepared.
Next, the resin dispersion and the colorant dispersion are mixed and stirred. At this time, if necessary, an aggregating agent such as an inorganic metal salt may be added while stirring.
By stirring for a predetermined time, an aggregate in which the resin material, the colorant and the like are aggregated is formed. As a result, a dispersion 6 in which the aggregate is dispersed as the dispersoid 61 is obtained.

  In the method for preparing a dispersion as described above, a kneaded material containing a resin material (binder resin) may be used. That is, as the “resin material” in the first method and the third method described above, a kneaded material containing a resin material may be used, or as the “powdered or granular material” in the second method, A kneaded material containing a resin material may be used. Thereby, for example, toner particles can be obtained as a mixture in which each constituent component is more uniformly mixed. In particular, even when the toner includes two or more components having poor dispersibility and compatibility, the above-described effects can be obtained. In addition, as a kneaded material, what contains components (for example, components, such as a coloring agent, a wax, a charge control agent) other than a resin component, for example can be used. Thereby, the above effects become more remarkable.

  Further, for example, the method described in Japanese Patent Application No. 2003-113428 may be applied to the preparation of the dispersion liquid 6. That is, a liquid containing a powdered or granular resin material (kneaded material) is ejected from a plurality of nozzles, the liquids ejected from the nozzles collide with each other, and the resin material (kneaded material) is atomized to form fine particles. A method of obtaining the dispersion 6 containing the dispersed dispersoid 61 may be applied. Thereby, the size of the dispersoid 61 contained in the dispersion liquid 6 can be easily made relatively small (the size in the above-described range), and the dispersion of the sizes of the dispersoids 61 can be easily achieved. Can be reduced.

  Further, it is preferable that the dispersion 6 obtained by the above method is subjected to a degassing treatment (subjected to a degassing step) before being used for discharge in a toner manufacturing apparatus described later. Thereby, the dissolved amount of the gas in the dispersion liquid 6 can be reduced, and when the dispersion medium 62 is removed from the dispersion liquid 6 ejected in the form of droplets in the transport unit of the toner manufacturing apparatus described later, It is possible to effectively prevent bubbles and the like from being generated in the dispersion liquid 6. As a result, it is possible to effectively prevent toner particles having irregular shapes (hollow particles, missing particles, etc.) from being mixed into the finally obtained toner. Therefore, it is possible to easily and reliably obtain a toner in which each toner particle has a uniform shape and a narrow particle size distribution. Thereby, the finally obtained toner can be made particularly excellent in properties such as transferability, fluidity, and cleaning properties. Further, by subjecting the dispersion liquid 6 to deaeration treatment, the ratio of pores (voids) in the finally obtained toner particles can be reduced. As a result, the reliability of the toner is further improved.

The method of deaeration treatment is not particularly limited, and for example, a method of applying ultrasonic vibration to the dispersion (ultrasonic vibration method), a method of placing the dispersion in a reduced-pressure atmosphere (decompression method), or the like can be used. .
When the decompression method is used as the degassing method, the pressure of the atmosphere in which the dispersion is placed is preferably 80 kPa or less, more preferably 0.1 to 40 kPa, and further preferably 1 to 27 kPa. preferable. If the atmospheric pressure during the degassing treatment is within this range, the dissolved gas can be efficiently removed while maintaining the shape of the dispersoid 61 in the dispersion 6 sufficiently.

Hereinafter, a toner manufacturing method and a toner manufacturing apparatus using the above dispersion will be described in detail.
[Toner production equipment]
The toner manufacturing apparatus 1 includes a head unit 2 that discharges the dispersion liquid 6 (particularly, the dispersion liquid 6 that has been degassed) as described above as a discharge product, and a dispersion liquid supply that supplies the dispersion liquid 6 to the head unit 2. Manufactured by the unit 4, the transport unit 3 that transports the dispersion 6 (discharged material) ejected from the head unit 2, and the ozone applying unit 12 that applies ozone to the aggregate 90 formed by the transport unit 3. A recovery unit 5 that recovers the toner particles 9, and an ozone recovery unit 14 that recovers ozone (unreacted ozone) supplied to the transport unit 3. Then, the transport unit 3 removes the dispersion medium 62 from the droplet-like dispersion 6 (performs a dispersion medium removal step) to obtain an aggregate 90, and a plurality of parts constituting the aggregate 90 In addition to joining the dispersoids (performing the joining step), the second region 33 imparts ozone to the aggregate 90 (discharged material) (performs the ozone provision step). In the present specification, the term “discharged material” refers to a dispersion liquid discharged in the form of droplets or a substance derived from the dispersion (granular material). For example, the dispersion liquid discharged in the form of droplets In addition to the above, the concept includes those in which the dispersion medium is removed from the dispersion, and those in which the dispersoid constituting the dispersion is modified (for example, at least a part of the constituent materials of the dispersoid undergoes a polymerization reaction). It is. In the present specification, “dispersoid” to be joined (for example, melt-bonded) in the joining step refers to the dispersoid constituting the dispersion or derived therefrom, for example, constituting the dispersion. In addition to the dispersoid itself, a part of the dispersoid from which a part of the component (for example, a solvent) has been removed, a part of at least a part of the constituent of the dispersoid denatured (for example, at least a constituent of the dispersoid This is a concept including a part of which undergoes a polymerization reaction.

The dispersion liquid supply unit 4 stores the dispersion liquid 6 as described above, and the dispersion liquid 6 is fed into the head unit 2.
The dispersion liquid supply unit 4 may have any function as long as it has a function of supplying the dispersion liquid 6 to the head unit 2. Alternatively, the dispersion liquid supply unit 4 may have stirring means 41 for stirring the dispersion liquid 6 as illustrated. Thereby, for example, even if the dispersoid 61 is difficult to disperse in the dispersion medium, the dispersion 6 in which the dispersoid 61 is sufficiently uniformly dispersed can be supplied into the head portion 2.
The head unit 2 includes a dispersion liquid storage unit 21, a piezoelectric element 22, and a discharge unit 23.
The dispersion liquid storage section 21 stores the dispersion liquid 6 as described above.
The dispersion liquid 6 stored in the dispersion liquid storage unit 21 is discharged from the discharge unit 23 to the transport unit 3 as a droplet-like discharge by a pressure pulse (piezoelectric pulse) of the piezoelectric element 22.

Thus, the present invention is characterized in that a dispersion is used. Thereby, for example, the following effects can be obtained.
That is, by using the dispersion liquid as the discharge liquid, when discharging the discharge liquid (dispersion liquid) from the discharge section, it is selectively cut at the portion of the dispersion medium that is microscopically low in viscosity and discharged as droplets. The For this reason, the size of the discharged dispersion liquid is small in variation in size among the droplets. Therefore, the finally obtained toner has a small variation in size among the particles (toner particles).

  And the droplet discharged from the discharge part becomes spherical shape immediately after discharge by the surface tension of the dispersion medium. Furthermore, even when the liquid droplets composed of the dispersion liquid are transported in the transport section, they have excellent shape stability and solidify while maintaining a substantially spherical shape. Therefore, the finally obtained toner (toner particles) has a high degree of circularity and a small variation in shape between particles (between toner particles).

  On the other hand, when a solution or a melt is used as the discharge liquid, such an effect cannot be obtained. That is, since such a discharge liquid has a uniform viscosity even when viewed microscopically, when the liquid is discharged from the discharge portion, the so-called liquid breakage is likely to be in a bad state, and the liquid droplets are tailed. It tends to be a shape that pulls. In addition, when it is transported in the transport section, it tends to have a shape with a tail as described above. Therefore, when a solution or a melt is used as the discharge liquid, the finally obtained toner has a large variation in size and shape between each particle (between toner particles) and a small degree of circularity of the toner particles. Easy to be.

  In addition, by using a dispersion as a discharge liquid, even when the toner particles to be produced have a sufficiently small particle size, the circularity is easily made sufficiently high and the particle size distribution is sharp. It can be. As a result, the resulting toner has a particularly high uniformity of charge among the particles, and when the toner is used for printing, a thin layer of toner formed on the developing roller is leveled and densified. Will be. As a result, defects such as fog are hardly generated and a sharper image can be formed. Further, since the shape and particle diameter of the toner particles are uniform, the bulk density of the whole toner (aggregate of toner particles) can be increased. As a result, it is advantageous for increasing the amount of toner filled in the cartridge of the same volume and for reducing the size of the cartridge.

Although the shape of the discharge part 23 is not specifically limited, It is preferable that it is a substantially circular shape. Thereby, the sphericity of the discharged dispersion liquid 6, the aggregate 90 formed in the transport unit 3, and the finally obtained toner particles 9 can be increased.
When the discharge part 23 is a substantially circular shape, the diameter (nozzle diameter) is, for example, preferably 5 to 500 μm, and more preferably 10 to 200 μm. If the diameter of the discharge part 23 is less than the lower limit, clogging is likely to occur, and the dispersion of the size of the discharged dispersion 6 (discharged material) may increase. On the other hand, when the diameter of the discharge part 23 exceeds the upper limit, the discharged dispersion liquid 6 may entrap bubbles depending on the force relationship between the negative pressure of the dispersion liquid storage part 21 and the surface tension of the nozzle. There is sex.

Further, the vicinity of the discharge portion 23 of the head portion 2 (particularly, the inner surface of the opening of the discharge portion 23 and the surface on the side where the discharge portion 23 of the head portion 2 is provided (the lower surface in the figure)) is a dispersion liquid. 6 preferably has liquid repellency. Thereby, it can prevent effectively that the dispersion liquid 6 adheres to the discharge part vicinity. As a result, it is possible to effectively prevent a so-called poor liquid runout or a discharge failure of the dispersion 6. Further, by effectively preventing the dispersion liquid 6 from adhering to the vicinity of the discharge portion, the stability of the shape of the discharged droplet is improved (the variation in shape and size among the droplets is small). Variation in the shape and size of the toner particles finally obtained is also reduced.
Examples of such a material having liquid repellency include fluorine resins such as polytetrafluoroethylene (PTFE), silicone materials, and the like.

  Further, the vicinity of the discharge portion 23 of the head portion 2 (particularly, the inner surface of the opening of the discharge portion 23 and the surface on the side where the discharge portion 23 of the head portion 2 is provided (the lower surface in the figure)) is hydrophobicized. It is preferable that the treatment is performed. Thereby, for example, when the dispersion medium 62 of the dispersion 6 is mainly composed of water, the above-described liquid repellency can be more suitably exhibited, and the above effects are more remarkable. Appears as something. Examples of the hydrophobic treatment method include formation of a film made of a hydrophobic material (for example, the above-described material having liquid repellency). By the way, water has a relatively high viscosity among various liquids, but even if such water is used as a constituent material of the dispersion medium 62, the disadvantage is caused by the dispersion 6 adhering to the vicinity of the discharge portion. Is effectively prevented from occurring. Therefore, when the hydrophobic treatment is performed in the vicinity of the discharge portion 23 of the head portion 2, the dispersion liquid 6 substantially not containing or hardly containing an organic solvent can be suitably used. The toner can be produced by a method that hardly causes an adverse effect.

As shown in FIG. 2, the piezoelectric element 22 includes a lower electrode (first electrode) 221, a piezoelectric body 222, and an upper electrode (second electrode) 223 that are stacked in this order. In other words, the piezoelectric element 22 has a configuration in which the piezoelectric body 222 is interposed between the upper electrode 223 and the lower electrode 221.
The piezoelectric element 22 functions as a vibration source, and the diaphragm 24 vibrates due to the vibration of the piezoelectric element (vibration source) 22 and has a function of instantaneously increasing the internal pressure of the dispersion liquid storage unit 21. It is.

  The head unit 2 is in a state where a predetermined ejection signal is not input from a piezoelectric element driving circuit (not shown), that is, a state where no voltage is applied between the lower electrode 221 and the upper electrode 223 of the piezoelectric element 22. Then, the piezoelectric body 222 is not deformed. For this reason, the diaphragm 24 is not deformed and the volume of the dispersion liquid storage unit 21 is not changed. Therefore, the dispersion 6 is not discharged from the discharge unit 23.

  On the other hand, in a state where a predetermined ejection signal is input from the piezoelectric element driving circuit, that is, in a state where a predetermined voltage is applied between the lower electrode 221 and the upper electrode 223 of the piezoelectric element 22, the piezoelectric body 222 is deformed. Arise. As a result, the diaphragm 24 is greatly deflected (bends downward in FIG. 2), and the volume of the dispersion liquid storage unit 21 is reduced (changed). At this time, the pressure in the dispersion liquid storage unit 21 increases instantaneously, and the granular dispersion liquid 6 is discharged from the discharge unit 23.

When one discharge of the dispersion liquid 6 is completed, the piezoelectric element driving circuit stops applying the voltage between the lower electrode 221 and the upper electrode 223. Thereby, the piezoelectric element 22 returns almost to its original shape, and the volume of the dispersion liquid storage unit 21 increases. At this time, a pressure (pressure in the positive direction) acting from the dispersion liquid supply unit 4 to the discharge unit 23 acts on the dispersion liquid 6. For this reason, air is prevented from entering the dispersion liquid storage part 21 from the discharge part 23, and an amount of the dispersion liquid 6 corresponding to the discharge amount of the dispersion liquid 6 is supplied from the dispersion liquid supply part 4 to the dispersion liquid storage part 21. The
By applying the voltage as described above at a predetermined cycle, the piezoelectric element 22 vibrates and the granular dispersion liquid 6 is repeatedly discharged.

In this way, by performing discharge (injection) of the dispersion liquid 6 with the pressure pulse generated by the vibration of the piezoelectric body 222, the dispersion liquid 6 can be intermittently discharged one by one, and the discharged dispersion liquid 6 can be discharged. The shape of is stable. As a result, it is possible to obtain a toner having a small variation in shape and size between each particle (each toner particle), and to produce toner particles having a high sphericity (geometrically perfect spherical shape). Can be made relatively easy.
Further, when the toner is manufactured by discharging the dispersion liquid as described above, the variation in particle diameter among the particles can be made particularly small, and the range of selection of the constituent material of the toner (particularly the binder resin) can be increased. Can be spread.

Further, by discharging (injecting) the dispersion liquid (discharged material) as described above, the vibration frequency of the piezoelectric body, the opening area (nozzle diameter) of the discharge portion, the temperature / viscosity of the dispersion liquid, and one drop of the dispersion liquid The amount of toner discharged, the content of the dispersoid in the dispersion, the particle size of the dispersoid in the dispersion can be controlled relatively accurately, and the toner particles to be manufactured can be controlled to the desired shape and size. Can be easily done. Further, by controlling these conditions and the like, for example, the production amount of toner and the like can be easily and reliably managed.
Further, by using the vibration of the piezoelectric body for discharging the dispersion liquid, the dispersion liquid can be discharged more reliably at a predetermined interval. For this reason, it can prevent effectively that the granular dispersion liquid (discharged material) discharged collides and aggregates, and can form the toner particle of a different shape more effectively.

The initial speed of the dispersion 6 (discharged material) discharged from the head unit 2 to the transport unit 3 is preferably, for example, 0.1 to 10 m / second, and more preferably 2 to 8 m / second. When the initial speed of the dispersion liquid 6 is less than the lower limit, the productivity of the toner decreases. On the other hand, when the initial velocity of the dispersion liquid 6 exceeds the upper limit, the sphericity of the finally obtained toner particles tends to decrease.
Moreover, the viscosity of the dispersion 6 discharged from the head part 2 is not particularly limited, but is preferably 0.5 to 200 [mPa · s], for example, 1 to 25 [mPa · s]. Is more preferable. If the viscosity of the dispersion liquid 6 is less than the lower limit, it is difficult to sufficiently control the size of the discharged dispersion liquid 6, and the dispersion of finally obtained toner particles may increase. On the other hand, when the viscosity of the dispersion 6 exceeds the upper limit, the diameter of the formed particles increases, the discharge speed of the dispersion 6 decreases, and the amount of energy required for discharging the dispersion 6 tends to increase. Show. In addition, when the viscosity of the dispersion liquid 6 is particularly large, the dispersion liquid 6 cannot be discharged as droplets.

  Further, the dispersion 6 discharged from the head unit 2 may be preheated. By heating the dispersion 6 in this manner, for example, even if the dispersoid 61 is in a solid state (or a relatively high viscosity state) at room temperature, the dispersoid is in a molten state (or in discharge). (Viscosity is relatively low, softened state). As a result, in the transport unit 3 to be described later, aggregation of the dispersoid 61 contained in the granular dispersion 6 and joining of the dispersoid 61 proceed smoothly, and the formed aggregate 90 has a particularly high degree of circularity. As a result, the toner particles finally obtained can also have a high degree of circularity.

Further, the dispersion 6 discharged from the head unit 2 may be cooled in advance. By cooling the dispersion 6 in this manner, for example, unintentional evaporation (volatilization) of the dispersion medium 62 from the dispersion 6 in the vicinity of the discharge unit 23 can be effectively prevented. As a result, it is possible to effectively prevent a change in the discharge amount of the dispersion liquid 6 due to a decrease in the opening area of the discharge portion over time, and a toner having a particularly small variation in size and shape between particles. Obtainable.
Further, the discharge amount of one drop of the dispersion 6 is slightly different depending on the content of the dispersoid 61 in the dispersion 6, but is preferably 0.05 to 500 pl, and more preferably 0.5 to 5 pl. Is more preferable. By setting the discharge amount of one drop of the dispersion 6 to a value in such a range, the formed aggregate 90 and toner particles 9 can have an appropriate particle size.

  Further, the average particle diameter of the dispersion 6 (discharged material) discharged from the head part 2 is slightly different depending on the content of the dispersoid 61 in the dispersion 6, but is preferably 2 to 50 μm. More preferably, it is ˜15 μm. By setting the average particle size of the dispersion 6 (discharged material) to a value in such a range, the formed aggregate 90 and toner particles 9 can be made to have appropriate particle sizes.

  Incidentally, the granular dispersion liquid 6 discharged from the head unit 2 is generally sufficiently larger than the dispersoid 61 in the dispersion liquid 6. That is, a large number of dispersoids 61 are dispersed in the granular dispersion liquid 6. For this reason, even if the dispersion of the particle size of the dispersoid 61 is relatively large, the ratio of the dispersoid 61 in the discharged granular dispersion liquid 6 is almost uniform for each droplet. Therefore, even when the dispersion of the particle size of the dispersoid 61 is relatively large, the toner particles 9 have a small variation in particle diameter among the particles by making the discharge amount of the dispersion 6 almost uniform. It becomes. Such a tendency becomes more prominent when the following relationship is satisfied. That is, when the average particle size of the discharged dispersion 6 is Dd [μm] and the average particle size of the dispersoid 61 in the dispersion 6 is Dm [μm], the relationship of Dm / Dd <0.5 is satisfied. It is preferable to satisfy the relationship of Dm / Dd <0.2.

  Further, when the average particle size of the discharged dispersion 6 is Dd [μm] and the average particle size of the manufactured toner particles is Dt [μm], a relationship of 0.05 ≦ Dt / Dd ≦ 1.0 is established. It is preferable to satisfy, and it is more preferable to satisfy the relationship of 0.1 ≦ Dt / Dd ≦ 0.8. By satisfying such a relationship, a sufficiently fine toner having a large circularity and a sharp particle size distribution can be obtained relatively easily.

  The frequency (frequency of the piezoelectric pulse) of the piezoelectric element 22 is not particularly limited, but is preferably 1 kHz to 500 MHz, and more preferably 5 kHz to 200 MHz. When the vibration frequency of the piezoelectric element 22 is less than the lower limit value, toner productivity decreases. On the other hand, when the vibration frequency of the piezoelectric element 22 exceeds the upper limit value, the discharge of the granular dispersion liquid 6 cannot follow, and the dispersion of the size of one drop of the dispersion liquid 6 may increase.

The toner manufacturing apparatus 1 having the illustrated configuration has a plurality of head portions 2. Then, a granular dispersion 6 is discharged from the head unit 2 to the transport unit 3.
Each head unit 2 may discharge the dispersion 6 almost simultaneously, but it is preferable that at least two adjacent head units are controlled so that the discharge timing of the dispersion 6 is different. . Thereby, before the granular dispersion liquid 6 (discharged material) discharged from the adjacent head part 2 solidifies (before becoming the aggregate 90), the granular dispersion liquid (discharged material) collide with each other, Aggregation can be more effectively prevented.

  Further, as shown in FIG. 2, the toner manufacturing apparatus 1 includes a gas flow supply unit 10, and the gas supplied from the gas flow supply unit 10 passes through the duct 101 to the head unit 2 -head. From each gas injection port 7 provided between the parts 2, it becomes the structure injected by a substantially uniform pressure. Thus, the aggregates 90 and the toner particles 9 can be obtained by conveying the ejections while maintaining the interval between the granular ejections (dispersion 6) intermittently ejected from the ejection unit 23. As a result, collision and aggregation of discharged granular dispersion liquids 6 (droplets) are more effectively prevented.

In addition, by injecting the gas supplied from the gas flow supply means 10 from the gas injection port 7, a gas flow that flows in substantially one direction (downward in the figure) can be formed in the transport unit 3. When such a gas flow is formed, the granular discharge (dispersion 6 and aggregate 90) in the transport unit 3 can be transported more efficiently.
Moreover, an airflow curtain is formed between the particles (discharged matter) discharged from each head part 2 by injecting gas from the gas injection port 7, for example, between each particle discharged from the adjacent head part It is possible to more effectively prevent collisions and agglomeration.

A heat exchanger 11 is attached to the gas flow supply means 10. Thereby, the temperature of the gas injected from the gas injection port 7 can be set to a preferable value, and the granular dispersion 6 discharged to the transport unit 3 can be solidified efficiently.
Further, when such a gas flow supply means 10 is provided, the solidification rate of the dispersion 6 discharged from the discharge unit 23 (the removal rate of the dispersion medium from the dispersion 6) is adjusted by adjusting the supply amount of the gas flow. Etc.) can be easily controlled.

  Although the temperature of the gas injected from the gas injection port 7 varies depending on the composition of the dispersoid 61 and the dispersion medium 62 contained in the dispersion 6, it is usually preferably 0 to 70 ° C., and 15 to 60 ° C. It is more preferable that When the temperature of the gas ejected from the gas ejection port 7 is in such a range, the dispersion 6 has a sufficiently high shape uniformity and stability of the obtained aggregate 90 and toner particles 9. The dispersion medium 62 contained therein can be efficiently removed.

  Moreover, the humidity of the gas injected from the gas injection port 7 is, for example, preferably 50% RH or less, and more preferably 10% RH or less. When the humidity of the gas injected from the gas injection port 7 is 50% RH or less, the dispersion medium 62 contained in the dispersion 6 is efficiently removed in the transport unit 3 (particularly, the first region 32) described later. Therefore, the toner productivity is further improved.

  The transport unit 3 includes a cylindrical housing 31, and includes a first region 32 and a second region along the transport direction of the discharged material (from the discharge unit 23 toward the recovery unit 5). 33. In the first region 32, a dispersion medium removal step (dispersion medium removal process) is performed in which the dispersion medium 62 is removed from the droplet-like dispersion liquid 6 to form an aggregate 90. Further, in the second region 33, a joining step (joining process) for joining a plurality of dispersoids constituting the aggregate 90 is performed. In particular, in the present embodiment, as described above, in the second region 33, the bonding process (bonding process) is performed, and the ozone applying process (ozone applying process) for applying ozone to the discharge (aggregate 90). Is done. That is, in the present embodiment, the bonding process and the ozone application process are performed in the same process (the same second region).

The first region 32 is normally set to a temperature lower than the temperature of the second region 33.
The temperature of the first region (low temperature region) 32 (treatment temperature in the dispersion medium removing step) varies depending on the composition of the dispersoid 61 and the dispersion medium 62 contained in the dispersion 6, but is usually 0 to 50 ° C. It is preferable and it is more preferable that it is 15-40 degreeC. When the temperature (atmosphere temperature) of the first region 32 is in such a range, the shape and uniformity of the shape of the obtained aggregate 90 are sufficiently high and contained in the dispersion 6. The dispersion medium 62 can be efficiently removed, and as a result, the toner productivity can be made particularly excellent. Further, since the formation of the aggregate 90 can proceed more smoothly, it is possible to contribute to the downsizing of the toner manufacturing apparatus 1.

When the temperature of the first region 32 (treatment temperature in the dispersion medium removing step) is T ₁ [° C.] and the glass transition point of the resin material constituting the dispersoid 61 is T _g [° C.], 0 ≦ T _It is preferable to satisfy the relationship of _g− T ₁ ≦ 70, more preferably to satisfy the relationship of 0 ≦ T _g −T ₁ ≦ 50, and to satisfy the relationship of 10 ≦ T _g −T ₁ ≦ 40. Further preferred. By satisfying such a relationship, it is possible to efficiently remove the dispersion medium 62 contained in the dispersion 6 while making the uniformity and stability of the shape of the obtained aggregate 90 sufficiently high, As a result, the productivity of the toner can be made particularly excellent. In the case in which the dispersoid 61 is composed of a plurality of kinds of resin material (resin component), a T _g, it is possible to employ a value determined as a weighted average of the weight of each of these components.

  The treatment time of the dispersion medium removing step as described above (the time from when the dispersion liquid 6 is jetted into droplets until the aggregate 90 is formed) is preferably 5 to 120 seconds, and 10 to 60 seconds. It is more preferable that it is 10 to 20 seconds. When the treatment time of the dispersion medium removal step is within such a range, the strength of the resulting aggregate 90 is sufficient (the aggregate 90 is decomposed and disintegrated before the toner particles 9 are manufactured). In this case, the toner productivity can be sufficiently increased.

  The granular dispersion 6 discharged from the head unit 2 becomes an aggregate 90 in which a plurality of dispersoids 61 are aggregated by removing the dispersion medium 62 while being transported through the first region 32. That is, as the dispersion medium 62 in the discharged dispersion liquid 6 is removed, the dispersoid 61 contained in the dispersion liquid 6 aggregates, and as a result, an aggregate 90 is obtained. Note that when the dispersoid 61 contains the solvent as described above, the solvent is usually also removed in the first region 32.

The aggregate 90 (discharged material subjected to the dispersion medium removal process) obtained in this step has the shape of the dispersion medium 62 until it is used for the joining process described later because most of the dispersion medium 62 has been removed. It can be retained sufficiently. In other words, the aggregate 90 obtained in this step may be stable enough to maintain its shape until it is used in the joining step. The part may remain. Even in such a case, the remaining dispersion medium and the like can be sufficiently removed by performing a joining step and the like as described later. Usually, the proportion of the constituent components of the dispersion medium contained in the aggregate 90 obtained in this step is 15 wt% or less.
The particle size of the dispersoid 61 contained in the dispersion 6 is usually sufficiently smaller than the obtained aggregate 90 (the granular dispersion 6 to be discharged). In other words, a large number of dispersoids 61 are contained in the obtained aggregate 90 (the granular dispersion 6 to be discharged). Therefore, the obtained aggregate 90 has a relatively large circularity.

In addition, since the dispersion medium 62 is removed in the transport unit 3 (first region 32), the obtained aggregate 90 is normally a droplet-like dispersion liquid 6 (discharged material) discharged from the discharge unit 23. Compared to For this reason, even if the area (opening area) of the discharge part 23 is relatively large, the size of the obtained aggregate 90 can be made relatively small. Therefore, even if the head portion 2 is not obtained by performing special precision processing (even if it can be manufactured relatively easily), sufficiently fine aggregates 90 and toner particles 9 are obtained. be able to.
Further, as described above, since the area of the discharge section 23 does not need to be extremely small, the particle size distribution of the dispersion 6 discharged from each head section 2 is made sufficiently sharp. be able to. As a result, the finally obtained toner also has a small variation in particle size between particles (between toner particles), that is, a sharp particle size distribution.

  Aggregates 90 (discharged material from which the dispersion medium 62 is removed) formed in the first region 32 are sent to the second region (high temperature region) 33, and a plurality of the aggregates 90 constituting the aggregate 90 are formed in this region. The dispersoid 61 is joined (joining step). By performing such treatment (bonding treatment), toner particles 9 having excellent mechanical stability can be obtained. That is, the above-described aggregate 90 has a relatively low bond strength between the dispersoids 61 constituting the aggregate 90 (bond strength between the dispersoid 61 and the dispersoid 61), so that a relatively small external force is applied. However, although disintegration (decomposition) is likely to occur, the toner particles 9 having excellent mechanical stability can be obtained by performing the joining process. In addition, the aggregate 90 has a large number of irregularities corresponding to the shape of the dispersoid 61 in the dispersion 6 in the vicinity of the surface thereof, and thus the circularity of the aggregate 90 is relatively large. However, by applying the bonding treatment to the aggregate 90, the above unevenness can be reduced, and the circularity of the finally obtained toner particles 9 can be made larger.

The joining process (joining process) is preferably performed by performing heat treatment on the aggregate 90 at a temperature equal to or higher than the treatment temperature in the dispersion medium removing process described above. Thereby, joining of the several dispersoid 61 which comprises the aggregate 90 can be advanced more effectively easily and reliably.
More specifically, the processing temperature (temperature of the first region 32) in the dispersion medium removing step is T ₁ [° C.], and the processing temperature in the joining step (temperature of the second region 33) is T ₂ [° C.]. Then, it is preferable to satisfy the relationship of 0 ≦ T ₂ −T ₁ ≦ 200, more preferably satisfy the relationship of 10 ≦ T ₂ −T ₁ ≦ 200, and 20 ≦ T ₂ −T ₁ ≦ 100. It is more preferable to satisfy the relationship, and it is most preferable to satisfy the relationship of 25 ≦ T ₂ −T ₁ ≦ 80. By satisfying such a relationship, the deterioration and modification of the constituent components are sufficiently prevented, the uniformity and stability of the shape of the obtained toner particles 9 are sufficiently high, and the circular shape of the toner particles 9 is further improved. The degree can be relatively large.

Further, when the treatment temperature in the joining step (joining treatment) is T ₂ [° C.] and the melting point of the resin material constituting the dispersoid 61 (dispersoid 61 constituting the aggregate 90) is T _m [° C.], − It is preferable that the relationship of 100 ≦ T ₂ −T _m ≦ 110 is satisfied, more preferably the relationship of −80 ≦ T ₂ −T _m ≦ 80 is satisfied, and the relationship of −50 ≦ T ₂ −T _m ≦ 70. Is more preferable, and it is most preferable that the relationship of −40 ≦ T ₂ −T _m ≦ 30 is satisfied. By satisfying such a relationship, the deterioration and modification of the constituent components are sufficiently prevented, the uniformity and stability of the shape of the obtained toner particles 9 are sufficiently high, and the circular shape of the toner particles 9 is further improved. The degree can be relatively large. In addition, when the resin material which comprises the dispersoid 61 (dispersoid 61 which comprises the aggregate 90) is comprised by multiple types of resin material (resin component), it is set as _Tm , and the weight of each of these components A value obtained as a reference weighted average value can be adopted.

  In addition, the specific value of the processing temperature (temperature of the second region 33) in the bonding process (bonding process) is not particularly limited, but a value within a range in which the processing time of the bonding process (bonding process) will be described later. In general, the temperature is preferably 50 to 200 ° C, more preferably 60 to 150 ° C. By satisfying such a relationship, the deterioration and modification of the constituent components are sufficiently prevented, the uniformity and stability of the shape of the obtained toner particles 9 are sufficiently high, and the circular shape of the toner particles 9 is further improved. The degree can be relatively large.

The processing time of the bonding process (bonding process) as described above is not particularly limited, but is 0.01 to 10 seconds when the processing temperature of the bonding process (bonding process) is a value within the range as described above. Is preferable, 0.05 to 10 seconds is more preferable, and 0.1 to 5 seconds is further preferable. When the processing time of the joining step is within such a range, the circularity of the toner particles 9 can be made sufficiently large while sufficiently preventing deterioration or modification of the constituent material of the toner.
In addition, as described above, in the second region, the joining process (joining process) as described above is performed, and the discharge product (aggregate 90 or a joined body in which a plurality of dispersoids constituting the aggregate 90 are joined). ) With ozone (ozone application process).

  As described above, the present invention is characterized in that ozone is applied in the production method using the dispersion. As described above, the dispersion liquid containing the constituent material of the toner generally contains a dispersant. By dispersing and removing the dispersant with ozone, the dispersion liquid has excellent charging characteristics and a uniform shape. The toner having a small particle size distribution can be produced efficiently and in an environmentally friendly manner. Further, by decomposing the dispersant with ozone, the toner finally obtained is excellent in environmental characteristics (water resistance and storage stability).

  On the other hand, if the dispersant is not removed, it will be difficult to obtain satisfactory charging characteristics in the finally obtained toner (more specifically, the absolute value of the charge amount of the toner particles should be sufficiently high). It is difficult to make it large, and variation in charging characteristics (charge amount) among toner particles tends to be large), and environmental characteristics (water resistance, storage stability) are also inferior. . This is presumably because the remaining dispersant neutralizes (inhibits) the charge of the toner resin, the charge control agent, or the like.

  By the way, even with a method that does not use ozone, it is conceivable to suppress the degree of decrease in the absolute value of the charge amount as described above, for example, by subjecting the obtained toner particles to a treatment such as washing. In such a case, a large amount of water (cleaning agent) is required for cleaning the toner particles, and the load on the environment is large. Further, even if the above-described cleaning is sufficiently performed, it is difficult to sufficiently solve the above-described problem, and the variation in the charge amount among the particles becomes large.

Moreover, the following effects are also acquired by using ozone for the removal of a dispersing agent.
That is, when ozone is used to remove the dispersant, the dispersant is usually decomposed (lower molecular weight) to low molecular weight compounds (for example, carbon dioxide, water, nitrogen, etc.). For this reason, the decomposed product of the dispersant easily volatilizes, and the adverse effect due to the remaining decomposed product remaining in the finally obtained toner is extremely unlikely to occur.

  The dispersant has a function of improving the dispersibility of the dispersoid in the dispersion, and is generally unevenly distributed near the surface of the dispersoid. In other words, the dispersant has a higher concentration (probability of existence) near the surface of the dispersoid than in the dispersoid and in the dispersion medium. Therefore, by applying ozone to the discharged material (aggregates as aggregates of a plurality of dispersoids), the dispersant that is unevenly distributed near the surface of the dispersoid (dispersoid constituting the discharged material) is selectively selected. It is possible to easily and surely prevent degradation and decomposition of the constituent material of the toner constituting the dispersoid (component to be contained in the toner) by decomposing and removing.

  In particular, in the present invention, by using a material having high ozone reactivity (having a molecular structure with a carbon-carbon unsaturated bond) as a dispersant, a constituent material of toner by ozone (should be included in the toner). The dispersant can be removed efficiently (selectively) while more effectively preventing adverse effects (degradation, degradation, etc.) on the component). That is, by using a dispersant having a molecular structure having a carbon-carbon unsaturated bond, the dispersant can be selectively decomposed without substantially causing degradation or deterioration of the constituent material of the toner. .

Moreover, in this invention, since the dispersing agent which has a molecular structure provided with the carbon-carbon unsaturated bond is used, a dispersing agent can be efficiently removed with a small amount and low concentration ozone. Thereby, it is possible to more effectively prevent the occurrence of adverse effects (decomposition degradation, etc.) on the constituent materials of the toner (components to be contained in the toner) such as the binder resin (resin material).
In addition, ozone is a substance having high reactivity with the dispersant as described above, and can disperse and remove the dispersant in a very small amount, but has low chemical stability in a normal environment. For this reason, even if ozone that could not contribute to the decomposition and removal of the dispersant leaks out of the toner production apparatus, the amount of ozone can be kept to a minimum, and in a relatively short time. Since it chemically changes to a highly safe substance (oxygen), etc., the possibility of adverse effects on the human body, environment, etc. is extremely low. In particular, in the present invention, since the dispersant having high reactivity with ozone is used, the amount and concentration of ozone can be reduced, and the possibility of adversely affecting the human body, environment, etc. can be further reduced. it can.

  In particular, as in the present embodiment, after removing the dispersion medium 62 from the discharge (dispersion 6), ozone is applied in the step of joining a plurality of dispersoids constituting the discharge (aggregate 90). In other words, by performing the bonding process and the ozone application process in the same process, ozone can be efficiently used for the decomposition and removal of the dispersant, so that the amount of ozone used can be further reduced. Moreover, since the 2nd area | region 33 which performs a joining process is set to comparatively high temperature, the reactivity of ozone becomes higher, As a result, the usage-amount of ozone can further be reduced.

Ozone is supplied into the transport unit 3 by the ozone applying means 12 and applied to the aggregate 90 in the second region 33.
The ozone applying unit 12 includes an injection port 121 that injects ozone in a direction opposite to the conveyance direction of the discharged material (dispersion 6, aggregate 90). Then, ozone is injected from the injection port 121 at a pressure higher than the pressure in the transport unit 3. By setting it as such a structure, ozone can be efficiently provided with respect to the aggregate 90 (discharged material), As a result, the usage-amount of ozone can be decreased.

The ozone used in the present invention may be in any form, for example, in the form of gas, solution (for example, ozone aqueous solution), but is preferably in the form of gas. Thereby, ozone in a homogeneous state can be more reliably applied to each discharge (aggregate 90). As a result, the finally obtained toner has a small variation in characteristics between each particle (between toner particles), and the reliability of the whole toner is improved.
The ozone supplied into the transport unit 3 may be substantially single ozone (ozone as a pure substance), or may be supplied as a mixture containing components other than ozone. However, the ozone reactivity can be more reliably controlled by supplying ozone as a mixture.

  The ozone concentration in the region where the ozone application step is performed (second region 33) is preferably 0.1 to 100 ppm, more preferably 0.5 to 50 ppm, and further preferably 1 to 30 ppm. preferable. When the ozone concentration is within the above range, it is possible to more efficiently decompose and remove the dispersant while more reliably preventing the deterioration of the constituent components (particularly, the binder resin) of the toner. On the other hand, if the ozone concentration is less than the lower limit, the time required to remove the dispersant becomes longer, and the toner productivity is lowered. In addition, the toner manufacturing apparatus is increased in size. If the ozone concentration exceeds the upper limit value, it may be difficult to selectively disassemble and remove the dispersant depending on the temperature of the region (second region 33) where the ozone application step is performed, and the toner constituent materials may deteriorate. May cause.

  The exposure time of the discharged matter (aggregate 90, toner particles 9) to ozone is preferably 0.1 to 30 minutes, more preferably 0.1 to 20 minutes, and 0.1 to 10 minutes. More preferably. When the exposure time to ozone is a value within the above range, the dispersant can be more efficiently decomposed and removed while more reliably preventing the deterioration of the constituent components (particularly, the binder resin) of the toner. On the other hand, if the exposure time to ozone is less than the lower limit, it may be difficult to sufficiently decompose and remove the dispersant depending on the content and type of the dispersant. If the exposure time to ozone exceeds the upper limit, depending on the content and type of the dispersant, there is a possibility that the constituent components (particularly binder resin, etc.) of the toner are deteriorated.

  As described above, in the present invention, the ozone application treatment can be suitably performed under relatively mild conditions (low ozone concentration, short time treatment). This is because a dispersant having a high reactivity with ozone is used, and this causes the constituent materials of the toner (components such as resin materials to be contained in the toner) to be decomposed and deteriorated by ozone. It is possible to selectively decompose and remove the dispersant selectively and effectively.

For the purpose of keeping the temperature of the first region 32 and the second region 33 within a predetermined range, for example, a heat source and a cooling source are installed inside or outside the housing 31 (the first region 32 and the second region 33). Alternatively, the housing 31 may be a jacket in which a flow path of a heat medium or a cooling medium is formed.
The pressure in the housing 31 (the first region 32 and the second region 33) depends on the amount of gas supplied by the gas flow supply means 10 and the gas (ozone supplied by the ozone applying means 12). Gas), the intake amount of the ozone recovery means 14 to be described later, and the like. As described above, by adjusting the pressure in the housing 31, the aggregate 90 and the toner particles 9 can be formed more efficiently, and as a result, the productivity of the toner is improved.

  Although the pressure in the housing 31 is not specifically limited, It is preferable that it is 150 kPa or less, It is more preferable that it is 100-120 kPa, It is further more preferable that it is 100-110 kPa. When the pressure in the housing 31 is a value within the above range, for example, abrupt removal of the dispersion medium 62 from the discharged material (bumping phenomenon) can be effectively prevented, and the irregularly shaped toner particles 9 can be prevented. The toner particles 9 can be more efficiently produced while sufficiently preventing the occurrence and the like. The pressure in the housing 31 may be substantially constant at each part or may be different at each part. For example, the first region 32 and the second region 33 may have different pressures.

The housing 31 is connected to voltage applying means 8 for applying a voltage. By applying a voltage having the same polarity as the granular discharge (dispersion 6, aggregate 90) to the inner surface side of the housing 31 by the voltage application unit 8, the following effects are obtained.
Usually, the toner particles and the aggregate 90 as the production intermediate thereof are positively or negatively charged. For this reason, if there is a charged substance charged with a polarity different from that of the aggregate 90, a phenomenon occurs in which the aggregate 90 is electrostatically attracted and attached to the charged substance. On the other hand, if there is a charged substance charged to the same polarity as the aggregate 90, the charged substance and the aggregate 90 repel each other, effectively preventing the phenomenon that the aggregate 90 adheres to the charged object surface. be able to. Therefore, by applying a voltage having the same polarity as the granular discharge (dispersion 6 and aggregate 90) to the inner surface of the housing 31, the discharge (dispersion 6 and aggregate 90) is applied to the inner surface of the housing 31. Adhesion can be effectively prevented. As a result, the generation of irregularly shaped toner particles can be more effectively prevented, and the collection efficiency of the toner particles 9 can be improved.

  Further, the housing 31 has a reduced diameter portion whose inner diameter decreases toward the collection unit 5 side (downstream side in the discharge material transport direction) and downward in FIG. 1 (downstream side in the discharge material transport direction). 311. By forming such a reduced diameter portion 311, it is possible to efficiently collect the toner particles 9. As described above, the dispersion 6 (discharged material) discharged from the discharge unit 23 becomes toner particles 9 through the aggregate 90 in the transport unit 3, but in the vicinity of the reduced diameter portion 311 in this way. The formation of the toner particles 9 is almost completely completed, and problems such as agglomeration hardly occur even when the particles contact each other.

  The toner particles 9 formed as described above are introduced into the cyclone 15 together with unreacted ozone and the like. The cyclone 15 is connected to the recovery unit 5 and is also connected to the ozone recovery means 14 via a bag filter 16 that prevents the toner particles 9 and the like from being sucked. As a result, the produced toner particles 9 are efficiently recovered by the recovery unit 5 and unreacted ozone is efficiently recovered by the ozone recovery means 14, in particular, while sufficiently preventing leakage from the apparatus. Can do. The ozone recovered by the ozone recovery means 14 can be sent, for example, to the ozone applying means 12 via a tube (not shown) and used for the ozone applying process (ozone applying process) described above. Thus, since the toner manufacturing apparatus 1 of the present embodiment has a configuration for collecting unreacted ozone, ozone can be efficiently used for manufacturing toner.

  The toner obtained as described above may be subjected to various kinds of treatment such as heat treatment as necessary. As a result, the joining of the dispersoids constituting the toner particles 9 is advanced, and the mechanical strength (mechanical stability) of the toner particles 9 is further improved, or the water content contained in the toner particles 9 is reduced. be able to. In addition, the water content contained in the toner particles 9 can be reduced in the same manner as described above by subjecting the obtained toner to a treatment such as aeration or leaving the toner in a reduced-pressure atmosphere. .

In addition, the toner as described above may be subjected to various processes such as a classification process and an external addition process as necessary.
For the classification treatment, for example, a sieve, an airflow classifier or the like can be used.
Examples of the external additive used for the external addition treatment include metal oxides such as silica, aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, titania, zinc oxide, alumina, and magnetite. , Nitrides such as silicon nitride, carbides such as silicon carbide, fine particles (inorganic fine particles) composed of inorganic materials such as calcium sulfate, calcium carbonate, aliphatic metal salts, acrylic resins, fluororesins, polystyrene resins, polyester resins, Examples thereof include fine particles (organic fine particles) composed of an organic material such as an aliphatic metal salt, and fine particles (composite fine particles) composed of a composite thereof. Examples of the composite fine particles include fine particles (granule) made of the inorganic material provided with a coating layer made of the organic material, and fine particles (granulate) made of the organic material. Examples thereof include fine particles provided with a coating layer made of a material.
Moreover, as an external additive, you may use what surface-treated with HMDS, a silane coupling agent, a titanate coupling agent, a fluorine-containing silane coupling agent, a silicone oil etc. on the surface.

The toner of the present invention produced as described above has a uniform shape and a sharp particle size distribution (small width). In particular, in the present invention, toner particles having a shape close to a true sphere can be obtained.
Specifically, the toner (toner particles) preferably has an average circularity R represented by the following formula (I) of 0.95 or more, more preferably 0.96 or more, and 0.97. More preferably, it is 0.98 or more. When the average circularity R is 0.95 or more, the toner transfer efficiency is further improved.
R = L ₀ / L ₁ (I)
(Where, L ₁ [μm] is the circumference of the projected image of the toner particles to be measured, and L ₀ [μm] is a perfect circle having an area equal to the area of the projected image of the toner particles to be measured (completely (Represents the perimeter of a geometric circle)

  In the toner, the standard deviation of the average circularity between each particle (between toner particles) is preferably 0.02 or less, more preferably 0.015 or less, and 0.01 or less. Is more preferable. When the standard deviation of the average circularity between the particles is 0.02 or less, variations in charging characteristics, fixing characteristics and the like are particularly small, and the reliability of the toner as a whole is further improved.

The average particle diameter based on the weight of the toner obtained as described above is preferably 2 to 20 μm, and more preferably 4 to 10 μm. When the average particle size of the toner is less than the lower limit, it becomes difficult to uniformly charge, and the adhesion force to the surface of the electrostatic latent image carrier (for example, a photoreceptor) increases. As a result, There may be an increase in the residual toner. On the other hand, when the average particle size of the toner exceeds the upper limit, the reproducibility of the contour portion of an image formed using the toner, particularly a character image or a light pattern, is deteriorated.
In addition, the toner preferably has a standard deviation in particle size between particles (between toner particles) of 1.5 μm or less, more preferably 1.3 μm or less, and 1.0 μm or less. Further preferred. When the standard deviation of the particle diameter between the particles is 1.5 μm or less, variations in charging characteristics, fixing characteristics and the like are particularly reduced, and the reliability of the toner as a whole is further improved.

  The water content (water content) of the toner particles 9 is not particularly limited, but is preferably 5 wt% or less, more preferably 0.01 to 4 wt%, and more preferably 0.02 to 1 wt%. Is more preferable. When the water content in the toner particles 9 is too large, there is a possibility that charging may become unstable. If the water content in the toner particles 9 is extremely reduced, the toner constituent materials are likely to be deteriorated or modified, and therefore it is not necessary to reduce the water content more than necessary.

<< Second Embodiment >>
Next, a second embodiment of the present invention will be described. Hereinafter, the present embodiment will be described with a focus on differences from the above-described embodiments, and description of similar matters will be omitted.
FIG. 3 is a longitudinal sectional view schematically showing a second embodiment of a toner manufacturing apparatus used for manufacturing the toner of the present invention.

  In the toner manufacturing apparatus 1 ′ of the present embodiment, the conveying unit 3 ′ removes the dispersion medium 62 from the droplet-like dispersion liquid 6 to obtain an aggregate 90 (performs a dispersion medium removal step), and discharges (dispersion) A first region 32 'for applying ozone to the liquid 6 and the aggregate 90) (performing an ozone applying step), and a second region 33' for joining a plurality of dispersoids constituting the aggregate 90; have. That is, the ozone application process (ozone application process) is performed in the first area in which the dispersion medium removal process (dispersion medium removal process) is performed, not in the second area in which the bonding process (bonding process) is performed. Except for this, it is the same as the first embodiment. In other words, the toner manufacturing apparatus of the present embodiment is the same as that of the first embodiment except that the ozone applying unit (jet port) is arranged to supply ozone to the first region. By setting it as such a structure, compared with embodiment mentioned above, the contact time of discharge matter (dispersion liquid 6, aggregate 90) and ozone can be lengthened. As a result, ozone can be efficiently used for removing the dispersant. Further, as described above, ozone is a substance having relatively low chemical stability. Therefore, by increasing the contact time between the discharged material and ozone, ozone can be efficiently used (consumed) in the transport unit 3, and ozone can be more reliably prevented from leaking out of the apparatus. it can. Further, in the first region 32, by applying ozone to the discharged material (particularly, the dispersion liquid 6 including the dispersion medium 62), the constituent material of the toner (component to be contained in the toner) comes into contact with ozone. Can be effectively prevented. As a result, the finally obtained toner is more reliable.

<< Third Embodiment >>
Next, a third embodiment of the present invention will be described. Hereinafter, the present embodiment will be described with a focus on differences from the above-described embodiments, and description of similar matters will be omitted.
FIG. 4 is a longitudinal sectional view schematically showing a third embodiment of a toner manufacturing apparatus used for manufacturing the toner of the present invention.

The toner manufacturing apparatus 1 '' of the present embodiment includes a bonded body storage unit 19 that stores (stores) the bonded body 95, and an ozone application processing unit 20 that performs an ozone applying process on the bonded body 95.
Further, in the toner manufacturing apparatus 1 ″ of the present embodiment, the cyclone 15 is connected to the joined body storage unit 19 via the double damper 18 and via the bag filter 16 that prevents the suction of the toner particles 9 and the like. It is also connected to the exhaust means 17. With such a configuration, the conveyance speed of the discharged material in the conveyance unit 3 can be adjusted more suitably, and the manufactured bonded body 95 can be efficiently fed into the bonded body storage unit 19.

  The joined body 95 discharged from the cyclone 15 is supplied to the joined body storage portion 19 via the double damper 18 and stored in the joined body storage portion 19. When a predetermined amount of the joined body 95 is stored in the joined body storage section 19, the joined body 95 in the joined body storage section 19 is supplied to the ozone application processing section 20 by opening the valve 191 that has been closed. Next, the valve 191 is closed again, and then a predetermined amount of ozone is supplied from the ozone applying means 12 while rotating the stirring means (propeller) 201 in the ozone applying treatment unit 20. As a result, the dispersant adhering to the bonded body 95 is decomposed and removed to form toner particles 9. Thus, in the present embodiment, the ozone application process is performed in a batch manner on a predetermined amount of the joined body 95 that has been once collected (stored). Thereby, since ozone can be used more efficiently for the decomposition and removal of the dispersant, the amount of ozone supplied when a predetermined amount of toner is manufactured can be reduced. Further, since the ozone supplied from the ozone applying means 12 can be efficiently applied to the bonded body 95, it is excellent from the viewpoint of saving resources and extending the life of the constituent members of the toner manufacturing apparatus. Further, in the present embodiment, ozone is supplied while stirring the joined body 95, so that ozone can be more uniformly applied to the entire outer surface of the joined body 95. As a result, the reliability of the finally obtained toner is further improved. In addition, the supply of ozone into the ozone application processing unit 20 may or may not be performed continuously during the ozone application process. For example, the configuration may be such that ozone is supplied in the initial stage of the ozone application process and then ozone is not supplied, or the ozone supply and the ozone supply stop are repeated. It may be.

  After the treatment with ozone for a predetermined time, the ozone recovery means 14 is driven in a state where the supply of ozone is stopped. Thereby, the ozone in the ozone provision process part 20 is collect | recovered. Since the bag filter 16 is disposed between the ozone recovery means 14 and the ozone application processing unit 20, it is possible to effectively prevent the manufactured toner particles 9 from being sucked. When ozone is collected by the ozone collecting means 14, outside air is introduced into the ozone application processing unit 20 by opening a valve (not shown) provided in the ozone application processing unit 20. The internal pressure may be adjusted.

  Thereafter, the driving of the ozone recovery means 14 is stopped, the injection valve 202 and the transport valve 203 are opened, an air flow (gas flow) from the injection valve 202 side to the transport valve 203 side is generated, and the toner in the ozone application processing unit 20 The particles 9 are sent to the collection unit 5. For example, the air flow (air flow from the injection valve 202 side to the transport valve 203 side) in the ozone application processing unit 20 sends gas into the ozone application processing unit 20 from the gas supply means 30 provided on the injection valve 202 side. Alternatively, it can be formed by exhausting the gas into the ozone application processing unit 20 by the exhaust means 40 provided on the transport valve 203 side. A filter (not shown) is provided between the gas supply means 30 and the ozone application processing unit 20 to prevent foreign matter from entering. In addition, a filter (not shown) is provided between the exhaust unit 40 and the ozone application processing unit 20 to prevent the suction of toner particles.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, each unit constituting the toner manufacturing apparatus can be replaced with an arbitrary one that exhibits the same function, or another configuration can be added.
Further, in the first and second embodiments described above, it has been described that ozone is jetted (supplied) in a direction opposite to the conveyance direction of the discharged matter (dispersion liquid, aggregate). It is not limited to what is injected (supplied) in such a direction.

  In the above-described embodiment, the ozone is described as being supplied (injected) from one injection port (supply port), but may be supplied from two or more injection ports (supply ports). For example, the first region and the second region may be configured to supply ozone. Moreover, in addition to the ozone provision process part demonstrated in 3rd Embodiment, the structure which supplies ozone also in a conveyance part may be sufficient.

  In the embodiment described above, the dispersion medium removal process (dispersion medium removal process), the ozone application process (ozone application process), and the bonding process (bonding process) are described as being performed continuously using the same apparatus. At least one of these processes may be performed by another apparatus. For example, the aggregate obtained by removing the dispersion medium from the dispersion discharged in the form of fine particles may be temporarily recovered, and the aggregate may be subjected to ozone applying treatment using another apparatus. Similarly, dispersoids (fine particles derived from dispersoids) constituting the aggregates are joined to form a joined body, and once this is recovered, the joined body is subjected to an ozone application treatment using another device. Also good. Similarly, after once collecting aggregates to which ozone has been applied, the aggregates may be subjected to a bonding process using another apparatus. Even in these cases, the same effect as described above can be obtained. Moreover, after collect | recovering the aggregates obtained as an intermediate body of a manufacturing process once, you may perform a subsequent process again using the same apparatus.

  Moreover, an ozone provision process (ozone provision process) may be performed as a pre-process (pre-process) of a dispersion medium removal process (dispersion medium removal process), for example. That is, after discharging the dispersion, before the dispersion medium is substantially removed (while maintaining the conditions such that the dispersion medium is not substantially removed by cooling or the like), ozone is applied to the discharged dispersion. Such a configuration may be adopted. Further, the ozone application process (ozone application process) may be performed as an intermediate process (intermediate process) between the dispersion medium removal process (dispersion medium removal process) and the bonding process (bonding process).

  In the present invention, a dispersant having a molecular structure having the carbon-carbon unsaturated bond as described above may be used. For example, the dispersant does not have the carbon-carbon unsaturated bond as described above. You may use together the substance of molecular structure as a structural component of a dispersing agent. In such a case, the content of the dispersant having the molecular structure having the carbon-carbon unsaturated bond as described above is preferably 50 wt% or more, and preferably 80 wt% or more. More preferably, it is 90-100 wt%.

Further, as shown in FIG. 5, an acoustic lens (concave lens) 25 may be installed in the head unit 2. By installing such an acoustic lens 25, for example, the pressure pulse (vibration energy) generated by the piezoelectric element 22 can be converged by the pressure pulse converging unit 26 in the vicinity of the ejection unit 23. As a result, vibration energy generated by the piezoelectric element 22 can be efficiently used as energy for discharging the dispersion liquid 6. Therefore, even if the dispersion liquid 6 stored in the dispersion liquid storage unit 21 has a relatively high viscosity, it can be reliably discharged from the discharge unit 23. In addition, even if the dispersion 6 stored in the dispersion storage unit 21 has a relatively large cohesive force (surface tension), it can be discharged as fine droplets. The particle diameter of the toner particles 9 can be controlled to a relatively small value.
As described above, the toner particles 9 can be formed in a desired shape and size even when a material having a higher viscosity or a material having a high cohesive force is used as the dispersion liquid 6 by adopting the configuration as illustrated. Therefore, the range of material selection is particularly wide, and a toner having desired characteristics can be obtained more easily.

  Further, in the case of the configuration shown in the figure, since the dispersion liquid 6 is ejected by the converged pressure pulse, the size of the dispersion liquid 6 to be ejected is large even when the area (opening area) of the ejection section 23 is relatively large. The thickness can be made relatively small. That is, even when it is desired to make the particle size of the toner particles 9 relatively small, the area of the discharge portion 23 can be increased. Thereby, even if the dispersion liquid 6 has a relatively high viscosity, the occurrence of clogging or the like in the discharge unit 23 can be more effectively prevented.

The acoustic lens is not limited to a concave lens, and for example, a Fresnel lens, an electronic scanning lens, or the like may be used.
Furthermore, as shown in FIGS. 6 to 8, a diaphragm member 13 or the like having a converging shape may be disposed between the acoustic lens 25 and the discharge unit 23 toward the discharge unit 23. Thereby, convergence of the pressure pulse (vibration energy) generated by the piezoelectric element 22 can be assisted, and the pressure pulse generated by the piezoelectric element 22 can be used more efficiently.
In the above-described embodiment, the toner component is described as a solid component contained in the dispersoid. However, at least a part of the toner component may be contained in the dispersion medium.

  In the above-described embodiment, the dispersion liquid is intermittently ejected from the head portion by the piezoelectric pulse. However, other methods can be used as a dispersion liquid ejection method (injection method). For example, as a method for discharging (injecting) the dispersion liquid, a method such as a spray drying method or a so-called bubble jet (“Bubble Jet” is a registered trademark) method is used, and “the dispersion liquid is pressed against a smooth surface with a gas flow. A method of injecting a dispersion into droplets using a nozzle that is thinly stretched to form a thin laminar flow and ejects the thin laminar flow as fine droplets away from the smooth surface (Japanese Patent Application No. 2002-321889). Or the like) ”or the like. The spray drying method is a method of obtaining liquid droplets by spraying (spraying) a liquid (dispersion) using a high-pressure gas. Moreover, as a method to which a so-called bubble jet (“bubble jet” is a registered trademark) method is applied, a method described in the specification of Japanese Patent Application No. 2002-169348 can be cited. That is, as a method for ejecting (injecting) the dispersion liquid, a “method for intermittently ejecting the dispersion liquid from the head portion by a change in gas volume” can be applied.

  Further, in the above-described embodiment, it has been described that ozone is applied during the dispersion medium removal step and / or after the dispersion medium removal step (after the dispersion liquid is discharged as droplet-like discharge matter). Ozone may be applied to the dispersion in the container instead of the discharged liquid (ozone may be applied batchwise). More specifically, a dispersion liquid (for example, a toner prepared by a polymerization method or the like) in a container containing a dispersoid having a desired size (a dispersoid adjusted to a size corresponding to the toner base particles to be manufactured). You may provide ozone with respect to the dispersion liquid containing the dispersoid corresponding to particle | grains. Thereby, the dispersant in the dispersion is decomposed and removed. Thus, when the dispersant is removed in the dispersion liquid in the container, the dispersoid cannot maintain the dispersion state, and settles or floats near the liquid surface. Particles corresponding to toner particles (toner mother particles) can be obtained by filtering the dispersoid. Then, you may perform various processes, such as drying, as needed. By adopting such a method, it is possible to efficiently produce toner using an apparatus with a simpler configuration (without using a large apparatus).

  In the above-described embodiment, the toner manufacturing apparatus of the present invention has been described as being used for manufacturing the toner itself. However, the present invention is not limited to this, and any toner can be used as long as it can be used for manufacturing powder for toner manufacturing. Good. For example, the toner production apparatus of the present invention produces a powder to be used as toner mother particles (toner mother particle production apparatus), and produces an aggregate obtained by removing the dispersant from the dispersion (aggregate production apparatus). Further, it may be one that manufactures a joined body from which the dispersant has been removed from an aggregate from which the dispersant has not been removed (joint body manufacturing apparatus).

[1] Production of toner (Example 1)
First, polyester resin as a binder resin (glass transition point Tg: 60.2 ° C., descending flow tester softening temperature: 102.8 ° C., melting point: 244 ° C., weight average molecular weight Mw (r): 8700): 200 weights Part and a phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight and Bontron E-84 as a charge control agent (manufactured by Orient Chemical Industries): 3 parts by weight did. The polyester resin used in this example had a molecular structure that did not have a carbon-carbon unsaturated bond in the molecule.

  On the other hand, lignin sulfonic acid (weight average molecular weight: 8000): 30 parts by weight and sodium alkyldiphenyl ether disulfonate (weight average molecular weight: 470): 0.5 parts by weight were dissolved in ion-exchanged water: 569.5 parts by weight. An aqueous solution (aqueous solution) was prepared. Weight average molecular weight Mw (d) for the dispersant (component A: 30 parts by weight and component B: 0.5 part by weight) used in the preparation of the aqueous liquid, and carbon present in one molecule The ratio (N (d) / Mw (d)) to the average value N (d) of the number of carbon unsaturated bonds was 0.0041. As Mw (d) and N (d), values obtained as weight-based weighted average values of the respective components (component A and component B) were adopted.

  Next, 600 parts by weight of this aqueous solution was placed in a 3 liter round bottom stainless steel container and stirred at a rotational speed of 4000 rpm while heating to 100 ° C. In the aqueous solution in this state, 215 parts by weight of the mixture (mixture of polyester resin, colorant and charge control agent) was added little by little, and after completion of the addition of the mixture, the mixture was further stirred for 5 minutes. Thereafter, the mixture was cooled to room temperature while continuing stirring, and a binder resin suspension (dispersion) in which solid dispersoids were dispersed was obtained.

  Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 38 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 180 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm. The average particle size of the dispersoid was measured using a laser diffraction / scattering type particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).

  The degassed dispersion (binder resin suspension) was put into a dispersion supply section of a toner production apparatus as shown in FIGS. While the dispersion liquid in the dispersion liquid supply part was stirred by the stirring means, the liquid was supplied to the dispersion liquid storage part of the head part by the metering pump, and was discharged from the discharge part to the transport part. The discharge part had a circular shape with a diameter of 25 μm. Further, as the head portion, a head portion that has been subjected to a hydrophobic treatment with a fluororesin (polytetrafluoroethylene) coat in the vicinity of the discharge portion is used.

  Dispersion liquid is discharged at a dispersion temperature of 40 ° C. in the head, the frequency of the piezoelectric body is 30 kHz, the initial speed of the dispersion discharged from the discharge section is 3 m / second, and one drop of the dispersion discharged from the head section. The discharge amount was adjusted to 4 pl (particle size Dd: 10 μm, weight: about 4 ng). Further, the dispersion liquid was discharged so that the discharge timing of the dispersion liquid was shifted in at least adjacent head parts among the plurality of head parts.

Further, when the dispersion liquid was discharged, air having a temperature of 40 ° C., a humidity of 27% RH, and a flow rate of 3 m / second was jetted vertically downward from the gas injection port. Further, the temperature (atmosphere temperature) in the housing is 35 to 40 ° C. in the first region, which is a region near the discharge unit, and 70 to 75 ° C. in the second region, which is a region near the collection unit. Was set to be. The pressure in the housing was about 101 kPa. The length of the first area (length in the transport direction) was 2 m, and the length of the second area (length in the transport direction) was 10 m.
On the other hand, from the injection port of the ozone applying means, a mixed gas of ozone and nitrogen is injected in a direction substantially opposite to the conveying direction of the dispersion liquid (discharged material), and ozone is supplied into the second region (FIG. 1). The gas mixture (ozone) was injected so that the ozone concentration in the second region was 10 ppm.

As a result, in the first region, the liquid dispersion in the form of droplets discharged toward the inside of the transport unit is removed to form an aggregate in which a plurality of dispersoids are aggregated (dispersion medium removal step). . Thereafter, the aggregate is subsequently conveyed to the second region, where a plurality of dispersoids constituting the aggregate are joined, ozone is applied, and the discharged matter (aggregate, joined body) The dispersant present near the surface was selectively decomposed and removed to form toner particles (ozone application and bonding step). The toner particles were introduced into a cyclone and then collected in a collection unit. Unreacted ozone supplied into the transport section was introduced into the cyclone together with the toner particles, and then recovered by the ozone recovery means via the bag filter. The ozone recovered in this way was reused in the ozone application process as described above. In addition, the processing time of the dispersion medium removing step (the time required for the ejected material to pass through the first region) for each particle (droplet and aggregate formed from the droplet) is 12 seconds. The treatment time of the ozone application and bonding process (the time required for the discharged material to pass through the second region) was 2 minutes. Further, the water content of the obtained toner particles was 3 wt%. The water content was measured by the Karl Fischer method.
Thereafter, the obtained toner particles were aerated at 50 ° C. for 1 hour to reduce the water content of the toner particles.

The toner particles obtained as described above had a water content of 0.6 wt%, an average circularity R of 0.95, and a circularity standard deviation of 0.019. The weight-based average particle diameter Dt was 7.0 μm. The particle size standard deviation based on weight was 0.82 μm. The circularity was measured in a water dispersion system using a flow particle image analyzer (manufactured by Toa Medical Electronics Co., Ltd., FPIA-2000). However, the circularity R is represented by the following formula (I).
R = L ₀ / L ₁ (I)
(Wherein, L ₁ [μm] is the circumference of the projected image of the particle to be measured, and L ₀ [μm] is the circumference of a perfect circle having an area equal to the area of the projected image of the particle to be measured. To express.)

(Examples 2 and 3)
As shown in Table 1, except for performing ozone application by changing the length of the transport unit (second region), and changing the processing time of the joining process (exposure time of the discharged material to the atmosphere containing ozone). Produced a toner in the same manner as in Example 1.

Example 4
First, polyurethane resin as a binder resin (glass transition point Tg: 50.4 ° C., descending flow tester softening temperature: 94.8 ° C., melting point: 167 ° C., weight average molecular weight Mw (r): 11500): 200 weight Parts, phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight, and Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) as a charge control agent: 3 parts by weight of toluene ( Wako Pure Chemical Industries, Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyurethane resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was produced in the same manner as in Example 1 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 5 and 6)
As shown in Table 1, except for performing ozone application by changing the length of the transport section (second region), and changing the processing time of the joining process (exposure time of the discharged material to the atmosphere containing ozone). Produced a toner in the same manner as in Example 4.

(Example 7)
First, a polyamide resin as a binder resin (glass transition point Tg: 69.7 ° C., descending flow tester softening temperature: 96 ° C., melting point: 225 ° C., weight average molecular weight Mw (r): 9000): 200 parts by weight , Phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight and Bontron E-84 as a charge control agent (manufactured by Orient Chemical Industries): 3 parts by weight (Manufactured by Yakuhin Co., Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyamide resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was produced in the same manner as in Example 1 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 8 and 9)
As shown in Table 1, except for performing ozone application by changing the length of the transport section (second region), and changing the processing time of the joining process (exposure time of the discharged material to the atmosphere containing ozone). Produced a toner in the same manner as in Example 7.

(Examples 10 to 12)
Toners were produced in the same manner as in Examples 1 to 3 except that polyester resins synthesized by changing the constituent monomers and polymerization conditions were used for preparing the binder resin suspension. The polyester resin used in this example had a glass transition point Tg of 65.2 ° C., a falling flow tester softening temperature of 108.2 ° C., a melting point of 251 ° C., and a weight average molecular weight Mw (r) of 8900. The average value N (r) of the number of carbon-carbon unsaturated bonds present in one molecule of the polyester resin used in this example was 0.0054.

(Examples 13 to 15)
By changing the blending ratio of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d), 1 molecule for the dispersant (mixture of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate) Example 10 except that the average value N (d) of the number of carbon-carbon unsaturated bonds present therein is changed and the value of N (d) / Mw (d) is as shown in Table 1. A toner was produced in the same manner.

(Example 16)
A toner was produced in the same manner as in Example 1 except that polystyrenesulfonic acid (weight average molecular weight: 10,000) was used instead of ligninsulfonic acid in the preparation of the aqueous solution. The weight average molecular weight Mw (d) of the dispersant (polystyrene sulfonic acid: 30 parts by weight and a mixture of sodium alkyldiphenyl ether disulfonate: 0.5 parts by weight) used in the preparation of the aqueous liquid, The ratio (N (d) / Mw (d)) of the number of carbon-carbon unsaturated bonds present to the average value N (d) was 0.0048. As Mw (d) and N (d), values obtained as weighted weighted average values of the respective components (polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate) were adopted.

(Examples 17 to 19)
By changing the blending ratio of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d) for the dispersant (mixture of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate), 1 molecule Example 16 except that the average value N (d) of the number of carbon-carbon unsaturated bonds present therein is changed and the value of N (d) / Mw (d) is as shown in Table 1. A toner was produced in the same manner.
(Example 20)
A toner was manufactured in the same manner as in Example 1 except that Bontron E-84 as a charge control agent was not used in the preparation of the binder resin solution (resin solution).

(Example 21)
First, in the same manner as in Example 1, a binder resin suspension (dispersion liquid) subjected to deaeration treatment was prepared.
The degassed dispersion (binder resin suspension) was put into a dispersion supply unit of a toner production apparatus as shown in FIGS. While the dispersion liquid in the dispersion liquid supply part was stirred by the stirring means, it was supplied to the dispersion liquid storage part of the head part by the metering pump and discharged from the discharge part to the transport part. The discharge part had a circular shape with a diameter of 25 μm. Further, as the head portion, a head portion that has been subjected to a hydrophobic treatment with a fluororesin (polytetrafluoroethylene) coat in the vicinity of the discharge portion is used.

  Dispersion liquid is discharged at a dispersion temperature of 40 ° C. in the head, the frequency of the piezoelectric body is 30 kHz, the initial speed of the dispersion discharged from the discharge section is 3 m / second, and one drop of the dispersion discharged from the head section. The discharge amount was adjusted to 4 pl (particle size Dd: 10 μm, weight: about 4 ng). Further, the dispersion liquid was discharged so that the discharge timing of the dispersion liquid was shifted in at least adjacent head parts among the plurality of head parts.

Further, when the dispersion liquid was discharged, air having a temperature of 40 ° C., a humidity of 27% RH, and a flow rate of 3 m / second was jetted vertically downward from the gas injection port. Further, the temperature (atmosphere temperature) in the housing is 35 to 40 ° C. in the first region, which is a region near the discharge unit, and 70 to 75 ° C. in the second region, which is a region near the collection unit. Was set to be. The pressure in the housing was about 101 kPa. The length of the first region (length in the transport direction) was 15 m, and the length of the second region (length in the transport direction) was 2 m.
On the other hand, from the injection port of the ozone applying means, a mixed gas of ozone and nitrogen is injected in a direction substantially opposite to the conveying direction of the dispersion liquid (discharged material), and ozone is supplied into the first region (FIG. 3). The gas mixture (ozone) was injected so that the ozone concentration in the first region was 10 ppm.

As a result, in the first region, the dispersion liquid in the form of liquid droplets discharged toward the conveying unit is removed with the dispersion medium, is provided with ozone, and a plurality of dispersoids are aggregated and dispersed. It became an aggregate from which the agent was removed (dispersion medium removal, ozone application step). Subsequently, the aggregate was subsequently conveyed to the second region, where a plurality of dispersoids constituting the aggregate were joined to form toner particles (joining step). The toner particles were introduced into a cyclone and then collected in a collection unit. Unreacted ozone (residue amount) of ozone supplied into the transport unit was introduced into the cyclone together with the toner particles, and then recovered by the ozone recovery means via the bag filter. Further, the processing time of the dispersion medium removing step (the time required for the discharged material to pass through the first region) for each particle (droplet and aggregate formed from the droplet) is 2 minutes. The treatment time for the ozone application and bonding process (the time required for the discharged material to pass through the second region) was 20 seconds. Further, the water content of the obtained toner particles was 3 wt%. The water content was measured by the Karl Fischer method.
Thereafter, the obtained toner particles were aerated at 50 ° C. for 1 hour to reduce the water content of the toner particles.
The toner particles obtained as described above had a water content of 0.8 wt%, an average circularity R of 0.94, and a circularity standard deviation of 0.018. The weight-based average particle diameter Dt was 8.3 μm. The particle size standard deviation based on weight was 0.76 μm.

(Examples 22 and 23)
As shown in Table 1, the dispersion medium removal by changing the length of the transport section (first region) and the treatment time of the ozone application process (exposure time of the discharged substance to the atmosphere containing ozone) are changed. A toner was manufactured in the same manner as in Example 21 except that.

(Example 24)
First, polyurethane resin as a binder resin (glass transition point Tg: 50.4 ° C., descending flow tester softening temperature: 94.8 ° C., melting point: 167 ° C., weight average molecular weight Mw (r): 11500): 200 weight Parts, phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight, and Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) as a charge control agent: 3 parts by weight of toluene ( Wako Pure Chemical Industries, Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyurethane resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was manufactured in the same manner as in Example 21 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 25 and 26)
As shown in Table 2, the dispersion medium removal by changing the length of the transport section (first region) and the treatment time of the ozone application process (exposure time of the discharged material to the atmosphere containing ozone) are changed. A toner was manufactured in the same manner as in Example 24 except that.

(Example 27)
First, a polyamide resin as a binder resin (glass transition point Tg: 69.7 ° C., descending flow tester softening temperature: 96 ° C., melting point: 225 ° C., weight average molecular weight Mw (r): 9000): 200 parts by weight , Phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight and Bontron E-84 as a charge control agent (manufactured by Orient Chemical Industries): 3 parts by weight (Manufactured by Yakuhin Co., Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyamide resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was manufactured in the same manner as in Example 21 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 28 and 29)
As shown in Table 2, the dispersion medium removal by changing the length of the transport section (first region) and the treatment time of the ozone application process (exposure time of the discharged material to the atmosphere containing ozone) are changed. A toner was manufactured in the same manner as in Example 27 except that.

(Examples 30 to 32)
Toners were produced in the same manner as in Examples 21 to 23 except that polyester resins synthesized by changing the constituent monomers and polymerization conditions were used for preparing the binder resin suspension. The polyester resin used in this example had a glass transition point Tg of 65.2 ° C., a falling flow tester softening temperature of 108.2 ° C., a melting point of 251 ° C., and a weight average molecular weight Mw (r) of 8900. The average value N (r) of the number of carbon-carbon unsaturated bonds present in one molecule of the polyester resin used in this example was 0.0054.

(Examples 33 to 35)
By changing the blending ratio of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d), 1 molecule for the dispersant (mixture of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate) Example 30 except that the average value N (d) of the number of carbon-carbon unsaturated bonds present therein is changed and the value of N (d) / Mw (d) is as shown in Table 2. A toner was produced in the same manner.

(Example 36)
A toner was produced in the same manner as in Example 21 except that polystyrene sulfonic acid (weight average molecular weight: 10,000) was used instead of lignin sulfonic acid in the preparation of the aqueous solution. The weight average molecular weight Mw (d) of the dispersant (polystyrene sulfonic acid: 30 parts by weight and a mixture of sodium alkyldiphenyl ether disulfonate: 0.5 parts by weight) used in the preparation of the aqueous liquid, The ratio (N (d) / Mw (d)) of the number of carbon-carbon unsaturated bonds present to the average value N (d) was 0.0048. As Mw (d) and N (d), values obtained as weighted weighted average values of the respective components (polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate) were adopted.

(Examples 37 to 39)
By changing the blending ratio of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d) for the dispersant (mixture of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate), 1 molecule Example 36, except that the average value N (d) of the number of carbon-carbon unsaturated bonds present therein is changed and the value of N (d) / Mw (d) is as shown in Table 2. A toner was produced in the same manner.
(Example 40)
A toner was manufactured in the same manner as in Example 21 except that Bontron E-84 as a charge control agent was not used in the preparation of the binder resin solution (resin solution).

(Example 41)
First, in the same manner as in Example 1, a binder resin suspension (dispersion liquid) subjected to deaeration treatment was prepared.
The degassed dispersion (binder resin suspension) was put into a dispersion supply unit of a toner production apparatus as shown in FIGS. While the dispersion liquid in the dispersion liquid supply part was stirred by the stirring means, it was supplied to the dispersion liquid storage part of the head part by the metering pump and discharged from the discharge part to the transport part. The discharge part had a circular shape with a diameter of 25 μm. Further, as the head portion, a head portion that has been subjected to a hydrophobic treatment with a fluororesin (polytetrafluoroethylene) coat in the vicinity of the discharge portion is used.

  Dispersion liquid is discharged at a dispersion temperature of 40 ° C. in the head, the frequency of the piezoelectric body is 30 kHz, the initial speed of the dispersion discharged from the discharge section is 3 m / second, and one drop of the dispersion discharged from the head section. The discharge amount was adjusted to 4 pl (particle size Dd: 10 μm, weight: about 4 ng). Further, the dispersion liquid was discharged so that the discharge timing of the dispersion liquid was shifted in at least adjacent head parts among the plurality of head parts.

  Further, at the time of discharging the dispersion, air having a temperature of 40 ° C., a humidity of 27% RH, and a flow velocity of 3 m / second was jetted vertically downward from the gas jetting port. Further, the temperature (atmosphere temperature) in the housing is 35 to 40 ° C. in the first region, which is a region near the discharge unit, and 70 to 75 ° C. in the second region, which is a region near the collection unit. Was set to be. The pressure in the housing was about 101 kPa. The length of the first region (length in the transport direction) was 2 m, and the length of the second region (length in the transport direction) was 3 m.

As a result, in the first region, the liquid dispersion in the form of droplets discharged toward the inside of the transport unit is removed to form an aggregate in which a plurality of dispersoids are aggregated (dispersion medium removal step). . Thereafter, the aggregate was subsequently conveyed to the second region, where a plurality of dispersoids constituting the aggregate were joined to form a joined body (joining step). Further, the processing time of the dispersion medium removing step (the time required for the ejected material to pass through the first region) for each particle (droplet and aggregate formed from the droplet) is 12 seconds. The processing time of the joining process (the time required for the discharged material to pass through the second region) was 0.5 minutes.
And the joined_body | zygote formed in the conveyance part was introduce | transduced into the cyclone, and was supplied in the ozone provision process part after that.

  In the ozone application treatment unit, ozone was applied to the joined body using the same ozone application means as used in Example 1 while stirring the joined body with the stirring means (propeller) (ozone application treatment). . The ozone application treatment was performed by injecting a mixed gas containing ozone and nitrogen so that the ozone concentration in the ozone application treatment section was 10 ppm. In addition, the rotation speed of the stirring means (propeller) was 180 rpm.

After performing the ozone application process as described above for 2 minutes, in a state where the supply of ozone into the ozone application process part is stopped, the ozone recovery means is driven to recover the ozone in the ozone application process part. The atmosphere was replaced with air.
Thereafter, the drive of the ozone recovery means is stopped, the injection valve and the transport valve are opened, the gas is supplied from the gas supply means provided on the injection valve side into the ozone application processing section, and the exhaust means provided on the transport valve side By exhausting the gas in the ozone application processing unit, an air flow (gas flow) from the injection valve side to the transport valve side was generated, and the toner particles in the ozone application processing unit were recovered by the recovery unit. The water content of the obtained toner particles was 3 wt%. The water content was measured by the Karl Fischer method.

Thereafter, the obtained toner particles were aerated at 50 ° C. for 1 hour to reduce the water content of the toner particles.
The toner particles obtained as described above had a water content of 0.5 wt%, an average circularity R of 0.96, and a circularity standard deviation of 0.014. The weight-based average particle diameter Dt was 6.6 μm. The particle size standard deviation based on weight was 0.73 μm.

(Examples 42 and 43)
As shown in Table 2, a toner was produced in the same manner as in Example 41 except that the treatment time of the ozone application process was changed.

(Example 44)
First, polyurethane resin as a binder resin (glass transition point Tg: 50.4 ° C., descending flow tester softening temperature: 94.8 ° C., melting point: 167 ° C., weight average molecular weight Mw (r): 11500): 200 weight Parts, phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight, and Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) as a charge control agent: 3 parts by weight of toluene ( Wako Pure Chemical Industries, Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyurethane resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was manufactured in the same manner as in Example 41 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 45 and 46)
A toner was produced in the same manner as in Example 44 except that the treatment time of the ozone application step (exposure time of the joined body to the atmosphere containing ozone) was changed as shown in Table 2.

(Example 47)
First, a polyamide resin as a binder resin (glass transition point Tg: 69.7 ° C., descending flow tester softening temperature: 96 ° C., melting point: 225 ° C., weight average molecular weight Mw (r): 9000): 200 parts by weight , Phthalocyanine pigment as a colorant (manufactured by Dainichi Seika Co., Ltd., phthalocyanine blue): 12 parts by weight and Bontron E-84 as a charge control agent (manufactured by Orient Chemical Industries): 3 parts by weight (Manufactured by Yakuhin Co., Ltd.): In addition to 800 parts by weight, the mixture was mixed at 75 ° C. Thereafter, they were further mixed by a ball mill to prepare a binder resin solution (resin solution). The polyamide resin used for the preparation of the binder resin solution had a molecular structure having no carbon-carbon unsaturated bond in the molecule.
On the other hand, an aqueous solution (aqueous solution) containing a dispersant was prepared in the same manner as in Example 1.

Next, 830.5 parts by weight of this aqueous solution is placed in a 3 liter round bottom stainless steel container, and the binder resin solution is stirred using a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) at a rotational speed of 4000 rpm. : 1015 parts by weight were gradually added dropwise over 10 minutes to obtain an emulsion. At this time, the liquid temperature was kept at 75 ° C.
Next, toluene in the emulsion (dispersoid) is removed (desolvent) under conditions of temperature: 45 ° C. and atmospheric pressure: 10-20 kPa, then cooled to room temperature, and further ion-exchanged water is added. As a result, a binder resin suspension (dispersion) in which the solid dispersoid was dispersed was obtained.

Thereafter, the obtained binder resin suspension (dispersion) was degassed. The deaeration treatment was performed by placing the binder resin suspension (dispersion) in a stirred state in an atmosphere of 14 kPa for 10 minutes. The ambient temperature during the deaeration treatment was 25 ° C. The solid content (dispersoid) concentration in the binder resin suspension (dispersion) thus obtained was 13 wt%. The viscosity of the binder resin suspension (dispersion) at 25 ° C. was 205 cps. Further, the average particle diameter Dm of the dispersoid constituting the binder resin suspension was 0.5 μm.
A toner was manufactured in the same manner as in Example 41 except that the dispersion liquid (binder resin suspension) obtained as described above was used as the discharge liquid.

(Examples 48 and 49)
A toner was produced in the same manner as in Example 47 except that the treatment time of the ozone application step (exposure time of the bonded body to the atmosphere containing ozone) was changed as shown in Table 3.
(Examples 50 to 52)
Toners were produced in the same manner as in Examples 41 to 43 except that polyester resins synthesized by changing the constituent monomers and polymerization conditions were used for preparing the binder resin suspension. The polyester resin used in this example had a glass transition point Tg of 65.2 ° C., a falling flow tester softening temperature of 108.2 ° C., a melting point of 251 ° C., and a weight average molecular weight Mw (r) of 8900. The average value N (r) of the number of carbon-carbon unsaturated bonds present in one molecule of the polyester resin used in this example was 0.0054.

(Examples 53 to 55)
By changing the blending ratio of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d), 1 molecule for the dispersant (mixture of lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate) Example 50 except that the average value N (d) of the number of carbon-carbon unsaturated bonds present therein is changed and the value of N (d) / Mw (d) is as shown in Table 3. A toner was produced in the same manner.

(Example 56)
A toner was produced in the same manner as in Example 41 except that polystyrene sulfonic acid (weight average molecular weight: 10,000) was used instead of lignin sulfonic acid in the preparation of the aqueous solution. The weight average molecular weight Mw (d) of the dispersant (polystyrene sulfonic acid: 30 parts by weight and a mixture of sodium alkyldiphenyl ether disulfonate: 0.5 parts by weight) used in the preparation of the aqueous liquid, The ratio (N (d) / Mw (d)) of the number of carbon-carbon unsaturated bonds present to the average value N (d) was 0.0048. As Mw (d) and N (d), values obtained as weighted weighted average values of the respective components (polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate) were adopted.

(Examples 57 to 59)
By changing the blending ratio of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate, the weight average molecular weight Mw (d) for the dispersant (mixture of polystyrene sulfonic acid and sodium alkyldiphenyl ether disulfonate), 1 molecule Example 56 except that the average value N (d) of the number of carbon-carbon unsaturated bonds existing in the inside was changed and the values of N (d) / Mw (d) were as shown in Table 3. A toner was produced in the same manner.
(Example 60)
A toner was manufactured in the same manner as in Example 41 except that Bontron E-84 as the charge control agent was not used in the preparation of the binder resin solution (resin solution).

(Comparative Example 1)
A toner was produced in the same manner as in Example 1 except that a toner production apparatus having the same configuration as that of the toner production apparatus used in Example 1 was used except that no ozone applying unit was provided.
(Comparative Example 2)
A toner was produced in the same manner as in Comparative Example 1 except that the dispersion (binder resin suspension) prepared in Example 4 was used.

(Comparative Example 3)
A toner was manufactured in the same manner as in Comparative Example 1 except that the dispersion (binder resin suspension) prepared in Example 7 was used.
(Comparative Example 4)
A toner was produced in the same manner as in Comparative Example 1 except that the dispersion (binder resin suspension) prepared in Example 16 was used.
(Comparative Example 5)
A toner was produced in the same manner as in Example 47 except that a toner production apparatus having the same configuration as the toner production apparatus used in Example 47 was used except that no ozone applying means was provided.

(Comparative Example 6)
Example 1 was used except that 30 parts by weight of lignin sulfonic acid and 30 parts by weight of polyethylene glycol (weight average molecular weight: 4800) were used instead of 0.5 parts by weight of sodium alkyldiphenyl ether disulfonate. A toner was produced. This dispersant has a molecular structure that does not have a carbon-carbon unsaturated bond.
(Comparative Example 7)
An attempt was made to produce a toner in the same manner as in Comparative Example 3 except that the binder resin solution (resin liquid) prepared in Example 7 was used as it was as a discharge liquid for toner production. The discharge was impossible. That is, in Comparative Example 7, the toner could not be manufactured.

(Comparative Example 8)
The toner obtained in Comparative Example 1 was washed with ion-exchanged water (washed with water) and then dried to obtain a final toner.
Washing with ion-exchanged water and drying were performed as follows.
First, in washing with ion-exchanged water, 100 parts by weight of ion-exchanged water was added to 1 part by weight of toner, and this was rotated at a rotational speed of 4000 rpm for 1 minute. Thereafter, washing water was removed by vacuum filtration. Such a series of operations (application of cleaning water, rotation, removal of cleaning water) was repeated twice. After the cleaning was completed by the above operation, the degree of vacuum was 2 torr and 40 ° C. using a vacuum dryer. For 5 hours, the drying process was performed until the water content became 0.7 wt% or less.
The above washing and drying required about 6 hours.

(Comparative Example 9)
A liquid for discharge (binder resin suspension) was prepared in the same manner as in Example 1 except that lignin sulfonic acid and sodium alkyldiphenyl ether disulfonate were not used. When the liquid is stirred with a relatively strong stirring force, the dispersoid can barely hold the structure dispersed in the dispersion medium. However, when the stirring is stopped, the solid particles corresponding to the dispersoid become liquid level. It floated in the vicinity and could not maintain the dispersed state. In addition, when the liquid was attempted to be discharged using the toner manufacturing apparatus used in Example 1, only water corresponding to the dispersion medium was discharged and solid particles corresponding to the dispersoid were discharged in the initial stage. Was not. In addition, when the liquid is continuously discharged, the discharge part is clogged with solid particles corresponding to the dispersoid floating near the liquid surface, and the liquid cannot be discharged. It was. That is, in Comparative Example 9, the toner could not be manufactured.
The toner particles obtained in Examples 1 to 60 were observed for their surface shapes using a scanning electron microscope (SEM). In the toner particles of Examples 1 to 60, no relatively large irregularities were observed on the surface, and it was confirmed that the toner particles had a substantially spherical shape.

  Tables 1 to 3 show toner production conditions for the above Examples and Comparative Examples. In Tables 1 to 3, a polyester resin having a glass transition point Tg: 60.2 ° C., a descending flow tester softening temperature: 102.8 ° C., and a melting point: 244 ° C. is PES-A, and a glass transition point Tg: 65. 2 ° C, descending flow tester softening temperature: 108.2 ° C, melting point: 251 ° C polyester resin PES-B, polyurethane resin PU, polyamide resin PA, lignin sulfonic acid A, alkyl diphenyl ether disulfonate sodium B Polystyrene sulfonic acid is indicated by C, polyethylene glycol is indicated by D, and the charge control agent is indicated by CCA.

[2] Evaluation Each toner obtained as described above was evaluated for charging characteristics, storage stability, durability, and transfer efficiency.
[2.1] Charging characteristics The toner of each Example and each Comparative Example was measured for the charge amount, and the standard deviation was obtained. The charge amount was measured using a suction type small charge amount measuring device (manufactured by Trek Japan) under the conditions of 20 ° C. and 62% RH.

[2.2] Preservability (environmental characteristics)
The toner of each Example and each Comparative Example was placed in a sample bottle in an amount of 10 g and left in a constant temperature bath at 50 ° C. and 85% RH for 48 hours. Then, the presence or absence of lumps (aggregation) was visually confirmed. The evaluation was made according to a three-stage standard.
A: The presence of lumps (aggregation) was not recognized at all.
○: Almost no lumps (aggregation) were observed.
(Triangle | delta): The small lump (aggregation) was recognized slightly.
X: A lump (aggregation) was clearly recognized.

[2.3] Durability The toner obtained in each of the above Examples and Comparative Examples was set in a developing machine of a color laser printer (manufactured by Seiko Epson Corporation: LP-2000C). Thereafter, the developing machine was continuously rotated so as not to print. After 12 hours, the developing machine was taken out, the uniformity of the toner thin layer on the developing roller was visually confirmed, and evaluated according to the following four criteria.

A: No disturbance is observed in the thin layer.
○: Disturbance is hardly observed in the thin layer.
Δ: Some disturbance is observed in the thin layer.
X: Streaky disturbance is clearly observed in the thin layer.

[2.4] Transfer Efficiency Transfer efficiency of each toner obtained as described above was evaluated.
Transfer efficiency was evaluated as follows using a color laser printer (manufactured by Seiko Epson Corporation, LP-2000C).
The toner on the photoconductor immediately after the development process to the photoconductor (before transfer) and the toner on the photoconductor after transfer (after printing) were collected using different tapes, and their weights were measured. When the toner weight on the photoconductor before transfer is W _b [g] and the toner weight on the photoconductor after transfer is W _a [g], it is obtained as (W _b −W _a ) × 100 / W _b. The value was defined as transfer efficiency.
The results are shown in Tables 4 to 8 together with the average circularity R, circularity standard deviation, weight-based average particle diameter Dt, and particle diameter standard deviation of the toner particles.

  As is apparent from Tables 4 to 8, all of the toners of the present invention (Examples 1 to 60) had a large absolute charge amount and small variations in the charge amount. In addition, the toner of the present invention was excellent in storage stability (environmental characteristics). The toner of the present invention was also excellent in properties such as durability and transfer efficiency. In addition, the toner of the present invention has small variations in size and shape between the particles, and the toner as a whole has high reliability.

On the other hand, satisfactory results were not obtained with the toners of the comparative examples.
In particular, in Comparative Examples 1 to 6, the absolute value of the charge amount of the toner particles was very small.
In Comparative Example 8, although the absolute value of the charge amount of the toner particles was relatively large, the charge amount variation among the particles was large, and the reliability of the toner as a whole was low. In addition, it takes a very long time to manufacture the toner, the productivity is inferior, and a large amount of waste water is generated, so the load on the environment is large.

  Further, the structure near the head of the toner manufacturing apparatus is changed from the structure shown in FIG. 2 to the structure shown in FIGS. 5 to 8, and the toner is manufactured and evaluated in the same manner as described above. As a result, the same result as above was obtained. In addition, in the toner manufacturing apparatus provided with the head portion as shown in FIGS. 5 to 8, even a dispersion liquid having a relatively high viscosity (a high dispersoid content) could be suitably discharged.

1 is a longitudinal sectional view schematically showing a first embodiment of a toner manufacturing apparatus used for manufacturing a toner of the present invention. FIG. 2 is an enlarged cross-sectional view of the vicinity of a head portion of the toner manufacturing apparatus shown in FIG. 1. FIG. 6 is a longitudinal sectional view schematically illustrating a second embodiment of a toner manufacturing apparatus used for manufacturing the toner of the present invention. FIG. 6 is a longitudinal sectional view schematically showing a third embodiment of a toner manufacturing apparatus used for manufacturing the toner of the present invention. FIG. 6 is a diagram schematically illustrating another example of the structure in the vicinity of the head portion of the toner manufacturing apparatus. FIG. 6 is a diagram schematically illustrating another example of the structure in the vicinity of the head portion of the toner manufacturing apparatus. FIG. 6 is a diagram schematically illustrating another example of the structure in the vicinity of the head portion of the toner manufacturing apparatus. FIG. 6 is a diagram schematically illustrating another example of the structure in the vicinity of the head portion of the toner manufacturing apparatus.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1, 1 ', 1' '... Toner manufacturing apparatus 2 ... Head part 21 ... Dispersion liquid storage part 22 ... Piezoelectric element 221 ... Lower electrode 222 ... Piezoelectric body 223 ... Upper electrode 23 ... Ejection part 24 ... Diaphragm 25 ... Acoustic lens (Concave surface lens) 26 ... pressure pulse converging unit 3, 3 ', 3' '... transport unit 31 ... housing 311 ... reduced diameter unit 32, 32' ... first region (low temperature region) 33, 33 '... second Region (high temperature region) 4 ... dispersion supply unit 41 ... stirring means 5 ... recovery unit 6 ... dispersion 61 ... dispersoid 62 ... dispersion medium 7 ... gas injection port 8 ... voltage application means 90 ... aggregate 95 ... junction 9 DESCRIPTION OF SYMBOLS Toner particle 10 ... Gas flow supply means 101 ... Duct 11 ... Heat exchanger 12 ... Ozone provision means 121 ... Injection port 13 ... Throttling member 14 ... Ozone collection means 15 ... Cyclone 16 ... Bag filter 1 ... exhaust means 18 ... double damper 19 ... joint member housing part 191 ... valve 20 ... ozone application treatment unit 201 ... stirring means (propeller) 202 ... injection valves 203 ... transportation valves 30 ... Gas supply means 40: exhaust means

Claims (24)

A method for producing a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and containing a dispersant having a function of improving the dispersibility of the dispersoid,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
A method for producing a toner, wherein ozone is applied during and / or after the dispersion medium removing step of removing the dispersion medium from the dispersion. A method for producing a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and containing a dispersant having a function of improving the dispersibility of the dispersoid,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
A method for producing toner, comprising: applying ozone to the discharge after the dispersion is discharged as a droplet-like discharge.   The method for producing a toner according to claim 2, wherein the discharged material includes a plurality of the dispersoids.   The method for producing toner according to claim 3, wherein after the dispersion medium removing step of removing the dispersion medium from the dispersion liquid, the ozone is applied in the step of joining the plurality of dispersoids constituting the discharged material. .   5. The toner manufacturing method according to claim 2, wherein in the dispersion medium removing step of removing the dispersion medium from the dispersion liquid, the ozone is applied to the discharged material.   6. The method for producing a toner according to claim 2, wherein the discharged material is exposed to an atmosphere containing ozone.   The toner production method according to claim 6, wherein the ozone concentration in the atmosphere is 0.1 to 100 ppm.   The method for producing a toner according to claim 6, wherein an exposure time of the discharged material to the atmosphere is 0.1 to 30 minutes.   The toner manufacturing method according to claim 1, wherein the dispersion liquid is intermittently ejected by a piezoelectric pulse. A method for producing a toner using a dispersion liquid in which a dispersoid containing a resin material is dispersed in a dispersion medium and containing a dispersant having a function of improving the dispersibility of the dispersoid,
As the dispersant, a dispersant having a molecular structure with a carbon-carbon unsaturated bond is used.
A method for producing toner, comprising the step of applying ozone to the dispersion.   The method for producing a toner according to claim 1, wherein the dispersion contains an anionic dispersant and / or a nonionic dispersant as the dispersant.   The method for producing a toner according to claim 1, wherein the content of the dispersant in the dispersant is 0.001 to 10 wt%.   The method for producing a toner according to claim 1, wherein the dispersion medium is mainly composed of water and / or a liquid having excellent compatibility with water.   The toner according to claim 1, wherein the dispersion contains a charge control agent.   The method for producing a toner according to claim 1, wherein the resin material has a molecular structure having no carbon-carbon unsaturated bond in the molecule.   When the weight average molecular weight of the dispersant is Mw (d) and the average number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d) [number], N (d) The toner production method according to claim 1, wherein a relationship of /Mw(d)≧0.003 is satisfied.   When the weight average molecular weight of the resin material is Mw (r) and the average number of carbon-carbon unsaturated bonds present in one molecule of the resin material is N (r) [number], N (r) The toner production method according to claim 1, wherein a relationship of /Mw(r)≦0.02 is satisfied.   The weight average molecular weight of the monomer unit of the dispersant is M (d), the average value of the number of carbon-carbon unsaturated bonds present in one molecule of the dispersant is N (d) [pieces], and When the weight average molecular weight is Mw (r) and the average number of carbon-carbon unsaturated bonds present in one molecule of the resin material is N (r) [number], [N (r) / Mw ( The toner production method according to claim 1, wherein a relationship of r)] / [N (d) / Mw (d)] ≦ 5 is satisfied.   A toner manufacturing apparatus used in the manufacturing method according to claim 1. A toner manufacturing apparatus includes: a discharge unit that discharges the dispersion;
The toner manufacturing apparatus according to claim 19, further comprising: an ozone applying unit that applies ozone to the dispersion liquid discharged from the discharge unit.   21. The apparatus according to claim 19 or 20, further comprising ozone applying means for removing ozone from the dispersion liquid and applying ozone to a granular dispersion medium removal product composed of a plurality of the dispersoids. Toner production equipment.   The toner manufacturing apparatus according to any one of claims 19 to 21, further comprising a region for joining a plurality of the dispersoids constituting the dispersion medium removal product.   A toner manufactured using the method according to claim 1.   23. A toner manufactured using the apparatus according to claim 19.

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