JP2017078749A - Manufacturing method of toner particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of toner capable of efficiently reducing a residual organic volatile substance in a toner when manufacturing toner particles with a wet method, and efficiently manufacturing toner particles having excellent image characteristics.SOLUTION: There is provided a manufacturing method of toner particles including: a granulation step of forming, in an aqueous medium, particles of a polymerizable monomer composition including a polymerizable monomer and a colorant; a polymerization step of polymerizing the polymerizable monomer included in the particles of the polymerizable monomer composition to obtain toner particles; and a distillation step of removing an organic volatile substance from a fluid dispersion of the toner particles, where the distillation step is performed under the ambient pressure, and the amount of water vapor to be supplied to the fluid dispersion of the toner particles is increased in the distillation step.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a toner and a toner particle manufacturing method for developing an electrostatic image in an image forming method such as electrophotography, electrostatic printing, and magnetic recording. In particular, when producing toner particles by a wet method, the present invention relates to a method for producing an electrophotographic toner that produces less foaming and coarse particles during the production, has less residual organic volatile components, and is excellent in environmental safety.

In recent years, as a method for producing toner particles, proposals have been made on wet toners such as a suspension polymerization method and an emulsion polymerization aggregation method using a mixture of a polymerizable monomer, a colorant, a release agent and the like.
The above-described wet toner is excellent in developability and transferability as compared with conventional pulverized toners due to characteristics such as inclusion of a release agent and characteristics such as easy control of the shape. However, it is difficult to completely remove residual organic volatile substances such as a polymerizable monomer and a solvent in the toner, and a small amount of residual organic volatile substances remain in the toner by either method. If the residual organic volatile substances remain in the toner, when the toner is used in an electrostatic image forming apparatus, the residual organic volatile substances are volatilized from the toner by heating and pressurizing at the time of image fixing, and an unpleasant odor is generated. Sometimes.

In recent years, regulations on residual organic volatile substances have become stricter worldwide, and it is required to reduce residual organic volatile substances even in wet toners.
On the other hand, in order to reduce residual organic volatile substances in wet toner, for example,
(I) a method of reducing residual organic volatile substances in a distillation step of the toner dispersion after polymerization,
(II) a method of reducing residual organic volatile substances in the drying process after dehydrating the toner dispersion;
Etc. are being considered.

As the method (I), a method of distilling off volatile organic compounds from toner particles by gradually or continuously increasing the amount of heat supplied to the aqueous dispersion of polymer particles after the polymerization under reduced pressure. Has been proposed (Patent Document 1).
Another method (I) is a method of supplying saturated water vapor to an aqueous dispersion of polymer particles at atmospheric pressure after the polymerization is completed, and distilling off volatile organic compounds from the toner particles. It has been proposed (Patent Document 2).

  On the other hand, in the method (II), toner particles generated by a wet method are supplied to a container for drying treatment, and then vacuum vapor is supplied into the container to remove residual organic volatile substances contained in the toner particles. A method has been proposed (Patent Document 3). In this method, it is described that the residual organic volatile substance can be effectively removed because an azeotropic action occurs in contact between the residual organic volatile substance and steam (Patent Document 3).

Japanese Patent No. 4092527 Japanese Patent No. 3332394 JP 2011-209429 A

  In the method described in Patent Document 1, since water vapor is supplied under reduced pressure in the distillation step, it is expected that foaming at the gas-liquid interface is very intense, and water vapor that sufficiently removes residual organic volatile substances is removed. It is expected that it cannot be supplied. Further, since the reduced-pressure steam is supplied, the temperature of the steam itself is low, and it is expected that the effect of reducing residual organic volatile substances by the steam is low.

  Compared to the method described in Patent Document 1, the method described in Patent Document 2 is operated at atmospheric pressure, so that the amount of water vapor / water vapor pressure to be input is expected to be large, and the effect of reducing residual organic volatile substances is high. I think that the. On the other hand, if water vapor is supplied in a state where the residual organic volatile substance concentration in the toner particle dispersion is high, the reason is not clear, but it is assumed that the residual organic volatile substance promotes coalescence between the toners, and the coarse particles May increase. Therefore, although this method has a high effect of removing residual organic volatile substances, it is expected that toner particles are likely to coalesce from the beginning to the middle of the distillation process where the concentration of residual organic volatile substances is high. Is expected to decline.

Further, recent toner particles respond to the demand for low-temperature fixability from the market with a low molecular weight and low Tg design. Therefore, in the method described in Patent Document 3 in which the toner particles are in direct contact with the vapor, it is difficult to suppress the coalescence of the toner or the elution of the release agent from the toner particles to a level required in the market in recent years. It is expected that image adverse effects such as sex will occur.
An object of the present invention is to provide a method for producing toner particles that solves the above-described problems.
That is, an object of the present invention is to provide a toner manufacturing method capable of efficiently reducing residual organic volatile substances in the toner.

As a result of intensive studies on means for efficiently reducing residual organic volatile substances in the toner, the present inventors have found the following method.
That is, the method for producing toner particles of the present invention includes:
A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition In a method for producing toner particles, comprising a polymerization step of obtaining toner particles by polymerizing a body, and a distillation step of removing organic volatile substances from the dispersion of the toner particles,
The distillation step is performed under atmospheric pressure;
In the distillation step, the amount of water vapor supplied to the dispersion liquid of the toner particles is increased.

  According to the present invention, it is possible to provide a toner manufacturing method capable of efficiently reducing organic volatile components remaining in toner particles in a short time while maintaining toner quality.

It is sectional drawing of the suitable container of this invention used at a distillation process. It is an example of a toner particle manufacturing flowchart used in the present invention.

The present invention can be suitably used in a method for producing toner particles by a wet method such as a suspension polymerization method using a polymerizable monomer or the like, or an emulsion polymerization aggregation method. As an example, the case where the present invention is used in a toner production method by a suspension polymerization method will be described below.
In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is added to an aqueous medium, the polymerizable monomer composition is granulated in the aqueous medium, and granulated. And a method for producing toner particles by polymerizing a polymerizable monomer contained in particles of the prepared polymerizable monomer composition.

<Preparation process of polymerizable monomer composition>
A polymerizable monomer composition containing at least a polymerizable monomer and a colorant is prepared. The colorant may be dispersed in the polymerizable monomer in advance with a medium stirring mill or the like and then mixed with another composition, or may be dispersed after mixing all the compositions.

<Granulation process>
The polymerizable monomer composition is put into an aqueous medium containing an inorganic dispersion stabilizer, granulated by dispersing, and the polymerizable monomer composition is formed by forming particles of the polymerizable monomer composition in the aqueous medium. A dispersion of body composition is obtained. The granulation step can be performed, for example, in a vertical stirring tank provided with a stirrer having a high shearing force. The following commercially available stirrers can be used as the stirrer having a high shearing force.
High shear mixer (manufactured by IKA), T. K. Homomixer (manufactured by PRIMIX CORPORATION), T. K. Philmix (manufactured by PRIMIX CORPORATION), CLEARMIX (manufactured by M Technique Co., Ltd.).

  Examples of the inorganic dispersion stabilizer include, for example, carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; metal phosphates such as aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate, and zinc phosphate; barium sulfate, sulfuric acid Examples thereof include sulfates such as calcium; metal hydroxides of calcium hydroxide, aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; These can be used alone or in combination of two or more. These exhibit functions as a dispersion stabilizer by being present as fine particles in an aqueous medium.

<Polymerization process>
By polymerizing the polymerizable monomer in the dispersion of the polymerizable monomer composition obtained by the granulation step, a polymer fine particle dispersion is obtained. In the polymerization step in the present invention, a general polymerization vessel having a stirring means and adjustable in temperature can be used.
The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C. The polymerization temperature may be constant throughout, but may be raised in the latter half of the polymerization step for the purpose of obtaining a desired molecular weight distribution. Any stirring means may be used as the stirring means used in the polymerization vessel as long as the dispersed polymerizable monomer composition is floated without stagnation and the temperature in the tank can be kept uniform.

As the stirring means, a stirring blade is suitable. For example, a general stirring blade such as a paddle blade, an inclined paddle blade, a three-blade retracted blade, a propeller blade, a disk turbine blade, a helical ribbon blade, and an anchor blade can be used. For example, the following products having high stirring performance are preferable.
Full Zone (manufactured by Shinko Environmental Solution Co., Ltd.), Twin Star (manufactured by Shinko Environmental Solution Co., Ltd.), Max Blend (manufactured by Sumitomo Heavy Industries, Ltd.), Supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi -F mixer (manufactured by Soken Chemical Co., Ltd.).

<Distillation process>
After the polymerization step is completed, in order to remove residual organic volatile substances such as unreacted polymerizable monomers and by-products, a part of the aqueous medium can be distilled off by a distillation step. Usually, the distillation step can be performed under atmospheric pressure or reduced pressure.In the present invention, however, as a result of intensive studies, the distillation step is performed while increasing the amount of water vapor introduced into the toner particle dispersion under atmospheric pressure. It has been found that doing this is effective in removing residual organic volatiles.

  In the case of distillation under reduced pressure, the amount of bubbles generated from the inside of the toner particle dispersion increases in proportion to the degree of vacuum. For this reason, it is difficult to suppress bumping compared to atmospheric pressure. Therefore, in order to suppress bumping under reduced pressure and stably carry out the distillation operation, the amount of water vapor introduced into the aqueous medium becomes smaller than that under atmospheric pressure. The amount of heat held by water vapor is proportional to the pressure, but under reduced pressure, the higher the water vapor, the more the volume expands, so it is more likely to bump, and low-flow, low-pressure water vapor is used for stable distillation. I have to. For the above reasons, distillation under reduced pressure cannot sufficiently remove organic volatile substances.

  On the other hand, distillation under atmospheric pressure allows high-pressure saturated steam to be introduced into an aqueous system, and the amount of heat retained by the steam increases in proportion to the pressure, so that the boiling point of an organic volatile substance having a boiling point of 100 ° C. or higher Effective for removal. However, the temperature of the water vapor increases in proportion to the pressure. However, if the temperature of the water vapor is too high, the coalescence of the toner particles becomes remarkable, the generation of coarse particles increases, and the problem of image defects and a decrease in yield. Produce. That is, how to introduce high-pressure and high-flow water vapor into an aqueous medium while suppressing coalescence of toner particles is an issue for efficiently carrying out the distillation process.

As a result of intensive studies, the present inventors have found that the total amount of organic volatile components contained in the toner particles and water vapor are effectively removed in order to efficiently remove residual organic volatile substances while suppressing coalescence of the toner particles during distillation. It was found that the relationship with the amount of heat supplied is important.
That is, in the present invention, when the heat supply amount of the water vapor is A (kJ / hr) and the total amount of organic volatile components contained in the toner particles is B (ppm),
At the start of the distillation step, the following formulas (1) and (2) are satisfied,
After increasing the amount of the water vapor, it is preferable to satisfy the following formulas (3) and (4).
Formula (1) 500 ≦ B
Formula (2) 385 <= A <= 525
Formula (3) B <= 200
Formula (4) 625 ≦ A ≦ 1625
The supply heat amount A (kJ / hr) of the water vapor means the heat amount per 1 kg of the polymer particles in the aqueous medium. In this case, the latent heat of water vapor (latent heat when water changes to water vapor) is 2259 kJ / kg, and the sensible heat of water vapor is 2 kJ / kg ° C.

When the total amount B of organic volatile components contained in the toner particles is 500 ppm or more and the supply heat amount A of the water vapor is 525 kJ / hr or less, the coalescence between the toner particles hardly occurs, which is preferable. The reason for this is not clear, but since the amount of organic volatile components contained in the toner particles is small, the surface of the toner is not easily plasticized. It seems that the electric repulsive force does not decrease.
When the particles are united, flat-shaped particles are generated. Particles that are flat compared to spherical particles differ in the adhesion of the external additive to the toner particle surface. Further, because of the flat shape, the fluidity of the toner is lower than that of a spherical shape. Therefore, in terms of electrophotographic characteristics, it is not preferable because the developability is reduced due to liberation of the external additive and the blur due to the decrease in fluidity is likely to occur.

  In addition, when B is 500 ppm or more and the supply heat amount A of water vapor is 385 kJ / hr or more, the supply heat amount into the aqueous medium is not too small, and the aqueous medium vaporizes with respect to the supplied heat amount. The ratio of the amount is not decreased, and the distillation efficiency is not significantly decreased. Further, the amount of the aqueous medium does not increase excessively during the distillation, and the steps after the distillation step do not become inefficient.

Further, it is preferable that the B is 200 ppm or less and the supply heat amount A of the water vapor is 1625 kJ / hr or less because the toner particles hardly coalesce. The reason is not clear, but the amount of heat supplied to the aqueous medium is not too large, so the toner particle surface does not melt or the viscosity does not drop significantly. This is probably because the coalescence of the toner particles is not promoted.
Further, when B is 200 ppm or less and the supply heat amount A of water vapor is 625 kJ / hr or more, the supply heat amount into the aqueous medium is not too small. For this reason, in order to reduce a residual organic volatile component to desired amount, distillation time does not take too much and distillation efficiency is not reduced significantly, and it is preferable.

  For the above reasons, in the present invention, in the distillation step, when the total amount B of organic volatile components contained in the toner particles is 500 ppm or more, the supply heat amount A of the water vapor is controlled to 385 kJ / hr or more and 525 kJ / hr or less. It is preferable to do. Further, when the total amount B of organic volatile components contained in the toner particles is in the range of 200 ppm or less, it is preferable to control the supply heat amount A of the water vapor to 625 kJ / hr or more and 1625 kJ / hr or less.

Further, as a result of intensive studies, the present inventors have found that the relationship between the heat supply A of the water vapor and the mass C (kg) of the aqueous medium in the distillation step is important in order to efficiently remove residual organic volatile substances. I found out. That is, in the present invention, it is preferable that A / C (kJ / kg · hr) satisfies the following formula (5).
Formula (5) 0.0385 <= A / C <= 0.1600

  In the present invention, when A / C is 0.1600 kJ / kg · hr or less, since the amount of water vapor with respect to the aqueous medium in the distillation tank is not excessive, a short path of water vapor does not occur inside the tank. . That is, this is preferable because the distillation efficiency per unit water vapor does not decrease. In addition, a large amount of water vapor supplied into the distillation tank is liquefied at once, and a large void is not generated due to volume reduction in the aqueous medium, and the stirring flow inside the tank is stabilized. As a result, the tank It is preferable because it does not vibrate itself and can be operated stably.

  On the other hand, when A / C is 0.0385 kJ / kg · hr or more, the amount of water vapor with respect to the aqueous medium in the distillation tank does not become excessive, and the water pressure due to stirring inside the tank and the head pressure of the aqueous medium itself And the supply pressure of water vapor do not antagonize. That is, it is not difficult to quantitatively supply water vapor into the distillation tank. As a result, it is preferable that a part of the aqueous medium does not flow back to the steam pipe, the efficiency of distillation is lowered, and further, the steam pipe and the valve are not blocked.

In the present invention, it is also a preferred method to perform a distillation operation while mixing an inert gas with the water vapor and introducing a mixed gas of the inert gas and saturated water vapor into the aqueous medium. The residual organic volatile component decreases in proportion to the amount of steam introduced, but if the amount exceeds a certain amount as described above, the distillation efficiency per unit steam volume decreases. Therefore, when a mixed gas obtained by mixing an inert gas with the water vapor is introduced in advance, the residual organic volatile components evaporated in the aqueous medium can be efficiently removed by causing the inert gas to act as a carrier gas. In addition, in the case of a mixed gas obtained by mixing an inert gas with the water vapor, the volume reduction rate inside the distillation tank is small compared to the water vapor alone, so that the stirring flow inside the tank is less disturbed and the vibration of the tank itself is also small. Therefore, it is preferable.
The distillation step is preferably performed until the total amount of organic volatile components contained in the toner particles at the time when the distillation step is completed is 50 ppm or less.

<Washing process, solid-liquid separation process and drying process>
In order to remove the dispersion stabilizer adhering to the surface of the polymer particles, the polymer particle dispersion can be treated with an acid or an alkali. Thereafter, the polymer particles are separated from the liquid phase by a general solid-liquid separation method. However, in order to completely remove the acid or alkali and the dispersion stabilizer component dissolved therein, water is added again to remove the polymer particles. Wash. This washing process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. The obtained toner particles are dried by a known drying means if necessary.

<Classification process>
The toner particles obtained in this way have a sufficiently sharp particle size as compared with conventional pulverized toners. However, when a sharper particle size is required, the toner particles are classified by an air classifier or the like. Particles deviating from the particle size distribution can be separated and removed.

<Polymerizable monomer>
As the polymerizable monomer suitably used in the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional or polyfunctional monomer can be used.

  Examples of the monofunctional polymerizable monomer include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate , Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, -Acrylic monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl Methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate Ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; Methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylol methane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene Glycol dimethacrylate, 1,3-buty Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . Among the above-described monomers, styrene or a styrene derivative is preferably used alone or in combination, or in combination with other monomers from the viewpoint of toner development characteristics and durability.

<Colorant>
Examples of the colorant preferably used in the present invention include the following organic pigments or dyes and inorganic pigments.
As the organic pigment or organic dye as the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used.
Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

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

As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used.
Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.
As the black colorant, carbon black and those which are toned in black using the yellow / magenta / cyan colorants are used.

These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the binder resin.
In selecting a colorant, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them. Preferably, these should be subjected to surface modification, for example, a hydrophobic treatment with a substance that does not inhibit polymerization. Examples of the surface treatment of the dye include a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to a raw material for toner such as a polymerizable monomer composition. . In addition to carbon black, the carbon black may be grafted with a substance that reacts with the surface functional groups of the carbon black, such as polyorganosiloxane.

<Release agent>
As the release agent used in the present invention, a wax in a solid state at room temperature may be used in terms of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.
Examples of the wax include the following. Polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof, and block compounds thereof. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter. In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used. The linear ester wax may be contained in an amount of 1 to 40 parts by weight, more preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.
In the present invention, a second release agent having a melting point lower than 80 ° C. can be used in combination in order to increase the plasticity of the toner particles and improve the fixability in the low temperature region. As the second release agent, a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester, or a montan derivative wax is preferably used. It is more preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

<Charge control agent>
The toner produced according to the present invention may contain a charge control agent. Known charge control agents can be used.
For example, the following are examples of toners that are controlled to be negatively charged. Organic metal compounds and chelate compounds are effective, monoazo dye metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, bisphenol and other phenol derivatives Kind. Furthermore, the following are mentioned. Urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, non-metallic carboxylic acids Compounds.

Examples of controlling the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and lake pigments thereof, tri Phenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide or ferrocyanide), higher fatty acid Metal salt. These can be used alone or in combination of two or more. Among these, charge control agents such as quaternary ammonium salts are particularly preferably used.
0.01-20 mass parts is preferable with respect to 100 mass parts of polymerizable monomers, and, as for the usage-amount of these charge control agents, 0.5-10 mass parts is more preferable.

<Polymerization initiator>
Examples of the polymerization initiator that can be used in the present invention include azo polymerization initiators. Examples of the azo polymerization initiator include the following. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis -4-methoxy-2,4-dimethylvaleronitrile, azobismethylbutyronitrile.

  An organic peroxide initiator can also be used. The following are mentioned as an organic peroxide type | system | group initiator. Benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.

  A redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides such as persulfates (sodium salts, potassium salts, ammonium salts, etc.), and oxidizing metal salts such as tetravalent cerium salts. Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts), ammonia, lower amines (amines having 1 to 6 carbon atoms such as methylamine and ethylamine), hydroxyl Amino compounds such as amines, sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, reducing sulfur compounds such as sodium formaldehyde sulfoxylate, lower alcohols (1 to 6 carbon atoms), ascorbic acid or salts thereof, And lower aldehyde (C1-6). The initiator is selected with reference to the 10-hour half-life temperature, and is used alone or in combination. Although the addition amount of this polymerization initiator changes with the target degree of polymerization, generally 0.5-20 mass parts is added with respect to 100 mass parts of polymerizable monomers.

<Crosslinking agent>
Various cross-linking agents can also be used in the present invention. The following are mentioned as a crosslinking agent. Divinylbenzene, 4,4′-divinylbiphenyl, hexanediol diacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate.

<Binder resin>
The binder resin used in the method for producing toner particles of the present invention is not particularly limited and may be appropriately selected from known ones. For example, styrenes such as styrene and chlorostyrene; ethylene, propylene, butylene Monoolefins such as isoprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl butyl ether; Shiruketon, vinyl ketones such as vinyl isopropenyl ketone, homopolymers such as, or a copolymer thereof.

  Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly p-chlorostyrene, and polyvinyl toluene. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  Particularly representative binder resins include, for example, polystyrene resins, polyester resins, styrene-alkyl acrylate copolymers, styrene-alkyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene. -Maleic anhydride copolymer, polyethylene resin, polypropylene resin and the like. These may be used individually by 1 type and may use 2 or more types together.

<External additive>
In the method for producing toner particles of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include the following. Metal oxide particles such as aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide; nitride particles such as silicon nitride; carbide particles such as carbide silicon carbide; Particles of inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate; particles of fatty acid metal salts such as zinc stearate and calcium stearate; particles of carbon black and silica.
These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of toner particles. The external additives may be used singly or in combination of two or more, but those subjected to hydrophobic treatment are more preferable.

<Magnetic material>
The method for producing toner particles of the present invention can also be applied to a method for producing a magnetic toner containing a magnetic material, and the magnetic material contained in the toner can also serve as a colorant. Examples of the magnetic material contained in the magnetic toner include the following. Iron oxides such as magnetite, hematite, ferrite; metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, Alloys of metals such as selenium, titanium, tungsten, vanadium and mixtures thereof.

These magnetic materials have a volume average particle diameter (Dv) of 0.5 μm or less, preferably about 0.1 to 0.5 μm.
The volume average particle diameter (Dv) of the magnetic body is a circle of the same area as the projected area of 100 magnetic bodies in the field of view at a magnification of 10,000 to 40,000 times using a transmission electron microscope (TEM). The equivalent diameter is obtained, and the volume average particle diameter is calculated based on the equivalent diameter.

The content of the magnetic substance in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer, and more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer. .
In addition, it is preferable that the magnetic material has a saturation magnetization (σs) of 50 to ²⁰⁰ Am ² / kg and a residual magnetization (σr) of ^{2 to} 20 Am ² / kg when 800 kA / m is applied. The magnetic properties of the magnetic material are measured using an oscillating magnetometer VSM P-1-10 (manufactured by Toei Industry Co., Ltd.) at a room temperature of 25 ° C. and an external magnetic field of 79.6 kA / m.

<Hydrophobicizing agent>
In order to improve the dispersibility of these magnetic materials in the toner particles, it is also preferable to subject the surface of the magnetic material to a hydrophobic treatment. Coupling agents such as a silane coupling agent and a titanium coupling agent are used for the hydrophobic treatment. Of these, silane coupling agents are preferably used. The following are mentioned as a silane coupling agent. Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxy Silane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane.

As described above, the toner produced according to the present invention can be used as either a one-component or two-component developer.
In the case of a magnetic toner containing a magnetic material in the toner as a one-component developer, a method of conveying or charging the magnetic toner using a magnet built in the developing sleeve is used. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly frictionally charge with a developing sleeve and the toner is attached to the sleeve to be conveyed.

  When the toner obtained by the production method of the present invention is used as a two-component developer, a carrier is used with the toner as a developer. Although it does not specifically limit as a carrier used for this invention, It is comprised by the single or composite ferrite state which mainly consists of iron, copper, zinc, nickel, cobalt, manganese, and a chromium atom.

The carrier shape is also important from the viewpoint that the saturation magnetization and electric resistance can be controlled over a wide range. For example, it is preferable to select a spherical shape, a flat shape, or an indeterminate shape, and to control the fine structure of the carrier surface state, for example, the surface unevenness. In general, a method is used in which a carrier core particle is generated in advance by firing and granulating the above metal compound, and then a resin is coated.
In order to reduce the load on the toner of the carrier, the following method can also be used.
A method of obtaining a low-density dispersion carrier by kneading and classifying a metal compound and a resin,
A method of obtaining a polymer carrier in which a kneaded product of a direct metal compound and a polymerizable monomer is suspension-polymerized in an aqueous medium and dispersed in a spherical shape.

The particle size of the carrier is measured based on the volume of the carrier using a laser diffraction particle size distribution measuring apparatus (Hellos <HELOS>) manufactured by SYNPATEC and equipped with a dry disperser (Rodos <RODOS>). Measured as median diameter.
The volume-based median diameter of these carriers is preferably 10 to 100 μm, and more preferably 20 to 50 μm.
In preparing the two-component developer, the mixing ratio of the carrier and the toner in the present invention is preferably 2% by mass to 15% by mass, and more preferably 4% by mass to 13% by mass as the toner concentration in the developer. If the toner concentration is 2% by mass or more, the image density is not too low, and if it is 15% by mass or less, image deterioration and increase in developer consumption caused by fogging and in-machine scattering do not occur.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but these do not limit the present invention in any way.
The measurement method used in the present invention will be described below.

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

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

On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter ( The value obtained by using the product) was set. The threshold value and the noise level were automatically set by pressing the “threshold / noise level measurement button”. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the “aperture tube flush after measurement” was checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.

1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
2) About 30 mL of the electrolytic solution is put into a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass.

3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 liters of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
4) The beaker of 2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

5) In a state where the electrolytic aqueous solution in the beaker of 4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
6) Into the round bottom beaker of 1) installed in the sample stand, the electrolyte solution of 5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. Measurement is performed until the number of measured particles reaches 50,000.

7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4), and set to graph / number%. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Method of measuring volume-based median diameter of sparingly water-soluble inorganic substance>
The volume-based median diameter (D50) of the fatty acid metal salt used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.
As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) The solvent refractive index of ion-exchanged water is set to 1.333. The refractive index of the hardly water-soluble inorganic compound is set depending on the sample.
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.
(7) A slightly water-soluble metal compound is added little by little, and the transmittance of the tungsten lamp is adjusted to 90% to 95%. Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

<Preparation of sample for measurement of residual organic volatiles>
In the case of measuring residual organic volatiles of toner particles in an aqueous medium, a toner dried in advance is prepared by the following procedure. The polymerization slurry or the distillation slurry is subjected to solid-liquid separation with a pressure filter. The filtration conditions at this time are as follows.
Cake thickness: 1.0-1.5cm
Pressurized air: 4.0 to 5.0 kg / cm ²
Filter paper: Kiriyama Seisakusho funnel filter NO. 5A
After solid-liquid separation under the above conditions, the sample is air-dried for about 30 minutes, and then dried by a constant temperature dryer at 45 ° C. for 1.0 hr to produce a measurement toner.

<Measurement of residual organic volatiles>
The amount of organic volatile component in terms of toluene of the toner by the headspace method can be measured as follows.
Weigh accurately 300 mg of toner in a headspace vial (volume: 22 mL), and seal with a crimp cap and a special septum coated with fluororesin using a crimper. This vial is set in a headspace sampler, and gas chromatogram (GC) analysis is performed under the following conditions. And the total area value of the peak of the obtained GC chart is calculated by data processing. At this time, an empty vial in which no toner is sealed is simultaneously measured as a blank, and a measurement value in the blank measurement is subtracted from the toner measurement data.

On the other hand, several vials (0.1 μL, 0.5 μL, 1.0 μL) prepared by precisely weighing toluene were prepared in the vial, and each measurement was performed under the following analysis conditions before measuring the toner sample. Then, a calibration curve is created from the amount of toluene charged and the toluene area value.
The amount of organic volatile component in terms of toluene can be obtained by converting the area value of the organic volatile component of the toner into the mass of toluene based on this calibration curve, and further converting it into an amount based on the toner mass.

<Measurement equipment and measurement conditions>
Headspace sampler: HEWLETT PACKARD 7694
Oven temperature: 150 ° C
Sample heating time: 60 minutes Sample loop (Ni): 1 mL
Loop temperature: 170 ° C
Transfer line temperature: 190 ° C
Pressurization time: 0.50 minutes LOOP FILL TIME: 0.01 minutes LOOP EQ TIME: 0.06 minutes INJECT TIME: 1.00 minutes GC cycle time: 80 minutes Carrier gas: He
GC: HEWLETT PACKARD 6890GC (detector: FID)
Column: HP-1 (inner diameter 0.25 μm × 30 m)
Oven: (1) 35 ° C .: Hold for 20 minutes, (2) Hold 20 ° C./min to 300 ° C. for 20 minutes Hold INJ: 300 ° C., Splitless, Constant Pressure (20 psi) Mode DET: 320 ° C.

<Coarse particles>
When the weight average particle diameter (D4) measured with the Coulter counter is measured, particles having a size of 12.0 μm or more are cut during wind classification because of low charging performance. That is, the larger the ratio of particles of 12.0 μm or more, the lower the productivity.

<Aspect ratio>
Measurement is performed with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation). The measurement principle is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with stroboscopic light with a nucleus for 1/60 second, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.19 μm × 0.19 μm per pixel), and the contour of each particle image is extracted, Long side: A short side distance or the like is measured.

The aspect ratio is the ratio of the long side to the short side of the particle image, and is calculated by the following equation.
Aspect ratio C = short side / long side When the particle image is circular, the aspect ratio becomes 1, and the larger the difference between the long and short sides, the more the particles are united and flattened. The ratio is small. After calculating the aspect ratio of each particle, an arithmetic average value of the obtained aspect ratio is calculated, and the value is defined as the average aspect ratio. The aspect ratio of the toner particles was measured with a flow particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

A specific measurement method is as follows.
First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.2 mL of a diluted solution obtained by diluting (made in ()) with ion-exchanged water about 3 times by mass is added.
Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, for example, the following ultrasonic disperser is used. A predetermined amount of ion-exchanged water is placed in a water tank, and about 2 mL of the contamination N is added to the water tank.
・ Ultrasonic Disperser “VS-150”, manufactured by VervoCrea Inc., oscillation frequency 50 kHz, electrical output 150 W, desktop type

  For the measurement, the flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens was used, and particle sheath “PSE-900A” (Sysmex Corporation) was used as the sheath liquid. Made). The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis was set to 85%, the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the toner particle aspect ratio was determined.

In measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm.

<Example 1>
Toner particles 1 were produced by the following procedure. The material was prepared at the following ratio so that the total amount of the aqueous medium and the polymerizable monomer composition was 10,000 kg.
(Preparation of aqueous medium)
Na ₃ PO ₄ : 5.3 parts by mass and 2.1% by mass of 10% hydrochloric acid are added to 380 parts by mass of ion-exchanged water, and the mixture is stirred at 2,500 s ⁻¹ using a high shear mixer (manufactured by IKA). While warming to 60 ° C. An aqueous solution in which 3.1 parts by mass of CaCl ₂ was dissolved in 32 parts by mass of ion-exchanged water was added thereto, and stirring and temperature control were continued for 60 minutes to prepare a calcium phosphate aqueous medium. At this time, when the weight average particle diameter of the produced calcium phosphate aqueous medium was measured by LA920, it was 0.15 μm.

(Preparation of polymerizable monomer composition)
The following materials were dissolved with a propeller type stirring device at 100 s ⁻¹ to prepare a solution.
Styrene 70.0 parts by mass n-butyl acrylate 15.0 parts by mass Polyester resin 5.0 parts by mass (terephthalic acid: isophthalic acid: propylene oxide modified bisphenol A (2 mol adduct): ethylene oxide modified bisphenol A ( 2 mol adduct) = 30: 30: 30: 10 (mass ratio) polycondensate, acid value 11 mgKOH / g, glass transition temperature Tg = 74 ° C., weight average molecular weight Mw = 11,000, number average molecular weight Mn = 4,000)
・ Low molecular weight polystyrene resin 15.0 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C.)
Next, the following materials were added to the solution.
Carbon black 7.0 parts by mass Negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 1.5 parts by mass Hydrocarbon wax having a melting point of 77 ° C. (HNP-51, manufactured by Nippon Seiwa Co., Ltd.) 10.0 parts by weight After the mixture was heated to 60 ° C., T.W. K. The mixture was stirred and dissolved and dispersed at 4,000 s ^{−1 with} a homomixer (manufactured by PRIMIX CORPORATION).
In this, 10.0 parts by mass of a polymerization initiator / perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)) was dissolved to prepare a polymerizable monomer composition.

(Granulation process)
The polymerizable monomer composition is charged into the aqueous medium and stirred at 2,500 s ⁻¹ for 30 minutes using a high shear mixer (manufactured by IKA) at a temperature of 60 ° C. A dispersion was obtained.

(Polymerization process)
After completion of the granulation step, the dispersion of the polymerizable monomer composition was transferred to a polymerization tank that was temperature-controlled at 60 ° C. After receiving the dispersion, stirring was started and the dispersion of the polymerizable monomer composition was heated to 70 ° C. After raising the temperature, the reaction was carried out at 70 ° C. for 5 hours. Subsequently, the temperature in the container 1 was raised to 85 ° C., and the reaction was further performed at 85 ° C. for 1 hour to obtain a polymerization slurry. After completion of the reaction, sampling was performed, and the total amount of residual organic volatiles in the toner particles [corresponding to B in the formula (1)] was measured. The results are shown in Table 1.

(Distillation process)
After completion of the polymerization process, the polymerization slurry was transferred to the distillation tank of FIG. 1 and stirring in the tank was started. At this time, when the inside of the tank was visually observed, no bubbles were present on the gas-liquid interface. Next, supply of water vapor was started at a flow rate of 475 kg / hr in the distillation tank while adjusting the opening of the water vapor valve 11.
At this time, the thermometer 12 and the pressure gauge 13 of the water vapor line displayed 200 kPa and 120 ° C., respectively. When this amount of water vapor is converted into the amount of heat supplied per kg of the toner component, it becomes 455 kJ / hr [corresponding to the amount of heat A supplied with water vapor in equation (2)].
After the temperature indicated by the thermometer 7 in the tank reached 100 ° C., it was confirmed that the vaporized aqueous medium was cooled by the condenser 15 and started to reflux to the condensation tank 14.
Even after the thermometer in the tank reaches 100 ° C., the supply of water vapor into the distillation tank is continued under the same conditions, and the amount of liquid recirculated in the condensing tank 14 is about 2 hr from the start of the temperature rise, It was 800 kg. At this time, the distillation slurry was sampled from the inside of the distillation vessel, and the residual organic volatile matter [corresponding to B in the formula (3)] in the toner particles was measured.

Next, supply of water vapor was started at a flow rate of 1000 kg / hr into the distillation tank while adjusting the opening of the water vapor valve 11.
At this time, the thermometer 12 and the pressure gauge 13 of the water vapor line displayed 200 kPa and 120 ° C., respectively. When this amount of water vapor is converted into the amount of heat supplied per kg of the toner component, it becomes 958 kJ / hr [corresponding to the amount of heat A supplied with water vapor in equation (4)].
Subsequently, the nitrogen valve 16 was gradually opened, and supply of nitrogen gas together with water vapor into the distillation tank was started from the nitrogen pipe 17. The flow rate of nitrogen gas at this time was adjusted to 5 L / min. Thereafter, the distillation operation was terminated when the distillation operation was continued for 3 hours.
At the end, the distillation slurry was sampled from the inside of the distillation vessel, and the residual organic volatiles in the toner particles were measured to find 20 ppm.

The particle size and spectroscopic ratio of the sample at the end of distillation were measured using a Coulter and FPIA3000. The ratio of the number of coarse particles having a weight average particle diameter D4 of 6.5 μm and 12 μm or more was 1.3%, and the aspect ratio was 0.923. As a result, toner coalescence hardly occurred during the distillation, and the distillation operation was satisfactory.
The state of foam in the tank during the distillation was foaming to such an extent that it did not become a problem.
After the distillation slurry was transferred, the inside of the water vapor valve in the tank and the inside of the pipe were visually checked. However, the adhesion of the toner was not confirmed, and no back flow of the liquid during distillation occurred.
Table 1 summarizes the distillation conditions and Table 2 summarizes the analysis results of the toner.

<Example 2>
The same operation as in Example 1 was performed, except that the nitrogen gas supplied during the distillation in Example 1 was not supplied. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 3>
The same operation as in Example 2 was performed except that the amount of water vapor supplied during the distillation in Example 2 was changed. Further, as in Example 2, the amount of water vapor was changed when the amount of liquid refluxed in the condensation tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 4>
The same operation as in Example 2 was performed except that the amount of water vapor supplied during the distillation in Example 2 was changed. Further, as in Example 2, the amount of water vapor was changed when the amount of liquid refluxed in the condensation tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 5>
(Polymerization process)
The same operation as in Example 1 was performed except that the polymerization temperature was changed as follows. After reacting the temperature during polymerization in Example 1 at 70 ° C. for 5 hours, the temperature elevation temperature was changed to 80 ° C. and the reaction was performed for 1 hour to obtain a polymerization slurry. After completion of the reaction, sampling was performed, and measurement of residual organic volatiles [corresponding to B in formula (1)] in the toner particles was 700 ppm. The results are shown in Table 2.

(Distillation process)
The same operation as in Example 3 was performed. Further, similarly to Example 3, the amount of water vapor was changed when the amount of liquid refluxed in the condensing tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 6>
The same operation as in Example 5 was performed except that the amount of water vapor supplied during the distillation in Example 5 was changed. Further, similarly to Example 5, the amount of water vapor was changed when the amount of liquid refluxed in the condensing tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 7>
The same operation as in Example 2 was performed except that the amount of water vapor supplied during the distillation in Example 2 was changed. Further, as in Example 2, the amount of water vapor was changed when the amount of liquid refluxed in the condensation tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Example 8>
The same operation as in Example 2 was performed except that the amount of water vapor supplied during the distillation in Example 2 was changed. Further, as in Example 2, the amount of water vapor was changed when the amount of liquid refluxed in the condensation tank 14 was 800 kg. The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Comparative Example 1>
The same operation as in Example 2 was performed except that the amount of water vapor supplied during the distillation in Example 2 was changed.
Further, the amount of water vapor during the distillation was examined at a constant amount from the start to the end.
When the inside of the tank was visually checked during the distillation, the entire gas-liquid interface was completely covered with thick foam, and when it reached 100 ° C., sudden boiling occurred and the condensation tank was almost filled with slurry. . The study was stopped at this point because it was difficult to continue the study. The distillation conditions are summarized in Table 1.

<Comparative example 2>
The same operation as Comparative Example 1 was performed except that the amount of water vapor supplied during the distillation of Comparative Example 1 was changed. At the end of the distillation, the distillation slurry was sampled from the inside of the distillation vessel and the residual organic volatiles in the toner particles were measured. As a result, the residual amount of residual organic compound was 150 ppm and the distillation was not performed efficiently. Seem.
The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Comparative Example 3>
The same operation as in Example 1 was performed until the polymerization step. After completion of the polymerization process, the polymerization slurry was transferred to the distillation tank of FIG. 1 and stirring in the tank was started. At this time, when the inside of the tank was visually observed, no bubbles were present on the gas-liquid interface. Next, supply of water vapor was started at a flow rate of 300 kg / hr in the distillation tank while adjusting the opening of the water vapor valve 11. At this time, the thermometer 12 and the pressure gauge 13 of the water vapor line displayed 200 kPa and 120 ° C., respectively. When this amount of water vapor is converted into the amount of heat supplied per kg of toner component, it becomes 287 kJ / hr [corresponding to the amount of heat A supplied with water vapor in equation (2)]. After the thermometer 7 in the tank reached 85 ° C., the pressure inside the tank started to be reduced from the vent line 18 and finally adjusted to 58 kPa as an absolute pressure.
When the temperature and pressure inside the distillation tank became stable, the inside of the polymerization tank was visually observed. Canceled.
<Comparative example 4>
The same operation as Comparative Example 1 was performed except that the amount of water vapor supplied during the distillation of Comparative Example 1 was changed. At the end of the distillation, the distillation slurry was sampled from the inside of the distillation vessel, and the residual organic volatiles in the toner particles were measured. Seem.
The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

<Reference Example 1>
The same operation as Comparative Example 1 was performed except that the amount of water vapor supplied during the distillation of Comparative Example 1 was changed. At the end of the distillation, the distillation slurry was sampled from the inside of the distillation vessel and the residual organic volatiles in the toner particles were measured. As a result, the residual amount of residual organic compound was as low as 30 ppm. On the other hand, when the aspect ratio of the toner particles was measured by FPIA 3000, it was a low value of 0.869, and it seems that many particles were united during distillation.
The distillation conditions are summarized in Table 1, and the toner analysis results are summarized in Table 2.

-Evaluation A regarding foaming: The state of foam in the tank during distillation was foaming to the extent that there was no particular problem.
B: During distillation, when the inside of the tank was visually confirmed, a lump of bubbles was confirmed at the central portion of the gas-liquid interface.
C1: When the inside of the tank was visually confirmed during distillation, foaming was confirmed over the entire gas-liquid interface.
C2: The state of bubbles in the tank at the beginning of distillation was that the entire gas-liquid interface was covered with a large amount of bubbles like soap bubbles. As a result of visual confirmation in the latter half of the distillation, the foam was reduced, and the foam was not particularly problematic.

Evaluation A regarding the adhesion of toner to the piping A: After the distillation slurry was transferred, the inside of the water vapor valve in the tank and the inside of the piping were visually checked. No toner adhesion was confirmed, and no back flow of the liquid during distillation occurred.
B: After the distillation slurry was transferred, the inside of the water vapor valve in the tank and the inside of the pipe were visually confirmed. The toner was very slightly attached to the inside of the pipe, but stable production was not difficult.
C: After the distillation slurry was transferred, the inside of the water vapor valve in the tank and the inside of the pipe were visually confirmed. The toner adhered to the valves and piping, and stable production was difficult.

1: container, 2: stirring blade, 3: baffle plate, 4: stirring motor, 5: gas-liquid interface, 6: jacket for temperature adjustment, 7: thermometer in distillation vessel, 8: jacket thermometer, 9: container Drain valve, 10: steam pipe, 11: steam valve, 12: steam thermometer, 13: steam pressure gauge, 14: condensation tank, 15: condenser, 16: nitrogen valve, 17: nitrogen pipe, 18 vent line

Claims (5)

A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a colorant in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition In a method for producing toner particles, comprising a polymerization step of obtaining toner particles by polymerizing a body, and a distillation step of removing organic volatile substances from the dispersion of the toner particles,
The distillation step is performed under atmospheric pressure;
A method for producing toner particles, comprising increasing the amount of water vapor supplied to the dispersion of toner particles in the distillation step. When the heat supply amount of the water vapor is A (kJ / hr) and the total amount of organic volatile components contained in the toner particles is B (ppm),
At the start of the distillation step, the following formulas (1) and (2) are satisfied,
The method for producing toner particles according to claim 1, wherein after the amount of the water vapor is increased, the following formulas (3) and (4) are satisfied.
Formula (1) 500 ≦ B
Formula (2) 385 <= A <= 525
Formula (3) B <= 200
Formula (4) 625 ≦ A ≦ 1625 The method for producing toner particles according to claim 1 or 2, wherein A / C (kJ / kg · hr) satisfies the following formula (5), where C (kg) is a mass of the aqueous medium in the distillation step.
Formula (5) 0.0385 <= A / C <= 0.1600   The method for producing toner particles according to claim 1, wherein an inert gas is mixed with the water vapor, and a mixed gas of the inert gas and water vapor is introduced into the aqueous medium. The method for producing toner particles according to claim 1, wherein the total amount of organic volatile components contained in the toner particles at the time when the distillation step is completed is 50 ppm or less.