JPH09319136A - Toner and developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color tone reproducibility, resolution and cleanability, to increase image density and to suppress fog by using a toner having specified mechanical strength. SOLUTION: This toner has 0.3-3.2kgf/mm<2> mechanical strength measured by a method represented by the formula, wherein P is load (kgf) causing 10% deformation and (d) is the particle diameter (mm) of the toner. It is produced, e.g. by mixing mother liquor for a toner contg. a bonding resin, a colorant and an org. solvent with an aq. soln. contg. a surfactant and an inorg. dispersant and then removing the org. solvent and water. The bonding resin is, e.g. a polyester resin or a vinyl polymer obtd. by polymerizing a polymerizable vinyl monomer such as styrene, its deriv. or an alkyl (meth)acrylate. The concn. of the solid components in the mother liquor is 25-55wt.%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to toners and developers useful in electrostatic image development.

[0002]

2. Description of the Related Art Electrophotography involves a charging step of applying a uniform electrostatic charge to a photoreceptor using a photoconductive substance, an exposure step of irradiating light to form an electrostatic latent image on the photoreceptor, A developing step of forming a toner image by attaching toner to the electrostatic latent image on the body, a transferring step of transferring the toner image to a support, and applying the toner image on the support to the support by heat, pressure, flash light, etc. This is a copying or recording technique that includes a fixing step for fixing, a cleaning step for removing toner remaining on the photoreceptor, and a charge removing step for removing an electrostatic charge on the photoreceptor and returning to an initial state. As many prints as possible can be made (US Pat. No. 2,297,691, British Patent 1,165,406 and British Patent 1,16).
5,405).

As a toner for developing an electrostatic image used in electrophotography, a toner using a polyester resin obtained by a condensation reaction of a glycol having a bisphenol skeleton and a polybasic acid (JP-A-61-7874). ), A toner using polystyrene resin (Japanese Patent Publication No. 44-16118).
JP-A-57-96354), a toner using a styrene-butyl methacrylate copolymer resin (Japanese Patent Publication No. 4-73444) and a toner using a bisphenol-type epoxy resin obtained by reacting bisphenol with epichlorohydrin. Is known.

In recent years, image formation using color toners has been required in place of conventional image formation using monochrome toners. On the other hand, in response to the trend toward higher density of information, a toner having a high resolution, that is, a toner having a small particle diameter capable of fine expression has been required. To meet such demands, a toner produced by a so-called pulverization method, in which a colorant and other additives are added to a low-molecular-weight polyester resin having excellent color tone reproducibility, and the mixture is melt-kneaded and then pulverized. Has been used. However, this toner has the following problems. (1) The dispersion of the colorant and other additives during melt-kneading is insufficient, and the color tone of the fixed image is not sufficient. Further, the composition of the toner becomes heterogeneous, and the image quality is not sufficient. (2) Finely pulverized particles are likely to be generated during stirring by a developing machine,
The image quality at the time of printing may be degraded, and toner may be scattered to contaminate the surrounding environment.

[0005]

The invention according to claim 1 provides a toner excellent in color tone reproducibility, resolution and cleaning property, high in image density and low in fogging. In addition to the effect of the invention described in claim 1, the invention described in claim 2 provides a toner excellent in durability against agitation by a developing machine. The invention according to claim 3 is the invention according to claim 2.
In addition to the effects of the invention described above, the present invention provides a toner having a narrow particle size distribution. The invention described in claim 4 provides a toner excellent in charging property in addition to the effect of the invention described in claim 2 or 3. The invention according to claim 5 is the invention according to claim 2.
In addition to the effect of the invention described in any one of 4 to 4, a toner having a narrower particle size distribution is provided. The invention according to claim 6 provides a developer having excellent color tone reproducibility, resolution and cleaning property, high image density, and little fog.

[0006]

Means for Solving the Problems The present invention includes the following (1) to
(6). (1) Formula (I)

[Equation 2] (In the formula, P represents a 10% deformation load (kgf), and d represents a toner particle diameter (mm)).
Toner that is ^{3 to} 3.2 (kgf / mm ² ). (2) The toner mother liquor containing a binder resin, a colorant and an organic solvent is mixed with an aqueous solution containing a surfactant and an inorganic dispersant, and then the organic solvent and water are removed to obtain the above (1). The toner described. (3) The solid content of the toner mother liquor is 25 to 55% by weight.
The toner according to (2) above.

(4) The concentration of the inorganic dispersant in the aqueous solution is 1 to
The toner according to (2) or (3) above, which is 10% by weight. (5) The toner according to any one of (2) to (4) above, wherein the content of the toner mother liquor with respect to the total amount of the toner mother liquor and the aqueous solution is 10 to 50% by weight. (6) A developer containing the toner according to any one of (1) to (5) and a carrier.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention has the formula (I)

(Equation 3) (In the formula, P represents a 10% deformation load (kgf), and d represents a toner particle diameter (mm)).
It is characterized by being 3 to 3.2 (kgf / mm ² ). With respect to the mechanical strength, for example, a toner fixed between an upper pressurizing indenter and a lower pressurizing plate is loaded at a constant increasing rate by an electromagnetic force or the like, and a toner particle diameter (mm) per one toner particle is The load (kgf) when deformed by 10% can be measured and calculated from the above formula (I).

In order to apply a load, for example, a flat diamond indenter having a diameter of 50 μm is provided on the upper part and SKS is provided on the lower part.
Using a micro compression tester (MCT type manufactured by Shimadzu Corp.) equipped with a pressure plate made of (alloy tool steel), the room temperature is 10 to 35.
It is possible to use a method of applying a load of 0.00145 gf / sec to each toner in a non-condensing atmosphere at a relative humidity of 30 to 80%. On the other hand, the particle size of the toner can be determined by measuring the particle size in the vertical and horizontal directions of the toner using an optical microscope attached to the tester, and taking the average value thereof. The mechanical strength can be obtained from these measured values,
Usually, the above-mentioned measurement is carried out for 10 to 20 toner particles, and the average value is taken as the mechanical strength of the toner.

The toner of the present invention has a mechanical strength of 0.3 to 3.2 (kgf / mm ² ) determined by the above formula (I),
From the viewpoint of the balance between the degree of occurrence of image defects and color reproducibility, 0.4 to 3 (kgf / mm ² ) is preferable,
It is more preferably 0.6 to 1 (kgf / mm ² ). If the mechanical strength is less than 0.3 (kgf / mm ² ), the toner in the developing machine is crushed by the stress in the developing machine and easily adheres firmly to the carrier surface. As a result, the charge amount of the toner decreases, Image defects such as toner scattering and fogging are likely to occur. On the other hand, this mechanical strength is 3.2 (kgf / m
When it exceeds m ² ), the fixability is poor and, as a result, the color reproducibility is poor.

In the toner of the present invention, for example, a toner mother liquor containing a binder resin, a colorant and an organic solvent is mixed with an aqueous solution containing a surfactant and an inorganic dispersant, and then the organic solvent and water are removed. Can be obtained by Examples of the binder resin used in the present invention include polyester resins and vinyl polymers obtained by polymerizing a polymerizable vinyl monomer. The polyester resin can be produced by a known synthesis method using an alcohol component and an acid component as raw materials.

Examples of the alcohol component include those represented by the general formula (II)

Embedded image (Wherein, R ¹ and R ² are ethylene groups or propylene groups, x and y are each an integer of 1 or more, and the sum of x and y is 4 to 14). Propylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3)-
2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -polyoxyethylene (2, 0) -2,2-
Bis (4-hydroxyphenyl) propane, etc.], ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, isopentyl glycol, hydrogenated bisphenol A, 1,3-butanediol,
1,4-butanediol, neopentyl glycol, xylylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, bis- (β-hydroxyethyl) terephthalate, tris- (β -Hydroxyethyl) isocyanurate, 2,2,4-trimethylolpentane-1,3-diol and the like.

Among these alcohol components, trihydric or higher alcohols are preferable from the viewpoint of stability such as fixing strength and offset resistance, but the blending amount is 40 mol% or less of the total alcohol components. The above alcohol components are used alone or in combination of two or more.

Examples of the acid component include malonic acid, succinic acid, glutaric acid, dimer acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, isophthalic acid dimethyl ester, terephthalic acid dimethyl ester, terephthalic acid monomethyl ester and tetrahydro. Phthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, dimethyltetrahydrophthalic acid, endomethylenehexahydrophthalic acid, naphthalenetetracarbic acid, diphenolic acid, trimellitic acid, pyromellitic acid, trimesic acid, cyclopentanedicarboxylic acid , 3,3 ', 4,4'
-Benzophenonetetracarboxylic acid, 1,2,3,4-
Butanetetracarboxylic acid, 2,2-bis- (4-carboxyphenyl) propane, anhydrides of these acids (maleic anhydride, trimellitic anhydride, etc.), trimellitic anhydride and 4,4-diaminophenylmethane Isocyanate ring obtained from trimerized reaction product of diimide carboxylic acid, tris- (β-carboxyethyl) isocyanurate, polyimide carboxylic acid containing isocyanurate ring, tolylene diisocyanate, xylylene diisocyanate or isophorone diisocyanate, and trimellitic anhydride Containing polyimide carboxylic acid.

Among these acid components, a carboxylic acid having a valence of 3 or more is preferable from the viewpoints of stability such as fixing strength and offset resistance, but the amount of the carboxylic acid is 40 mol% or less of the total acid components. The above acid components are used alone or in combination of two or more.

In addition to the alcohol component and the acid component, hydroxycarboxylic acid components (p-oxybenzoic acid, vanillic acid, dimethylolpropionic acid, malic acid, tartaric acid, 5
-Hydroxyisophthalic acid, etc.) can also be added,
When the hydroxycarboxylic acid component is added, its amount is 0.7 to 17 mol% of the total monomer components. The polyester resin is composed of the alcohol component and the acid component (in some cases,
Further, the above-mentioned hydroxycarboxylic acid component) can be produced by a condensation reaction according to a conventional method. For example, the alcohol component and the acid component are blended in a reaction vessel,
150 to 190 ° C in the presence of an inert gas (such as nitrogen gas)
At a temperature of 200 to 250 ° C. for 6 to 8 hours.
It can be manufactured by heating for a time and obtaining a reactant.

The alcohol component and the acid component can be blended in a range conventionally used, but they are usually blended in a ratio of 1/2 to 2/1 in terms of a hydroxyl group / carboxyl group molar ratio. The acid value of the obtained polyester resin is not particularly limited, but is usually 1 to 20.

A catalyst may be added during the production of the polyester resin. When the carboxylic acid component used is a free carboxylic acid containing no ester group, examples of the catalyst include esterification catalysts (dibutyltin dilaurate, dibutyltin oxide and other organic metals, and tetrabutyl titanate and other metal alkoxides). ) Can be used, and the amount thereof is preferably 0.1 to 1% by weight based on the total amount of the raw materials. When the carboxylic acid component is a lower alkyl ester, examples of the catalyst include transesterification catalysts (metal acetates such as zinc acetate, lead acetate and magnesium acetate, metal oxides such as zinc oxide and antimony oxide, and tetraoxides). Metal alkoxides such as butyl titanate) can be used, and the compounding amount thereof is 0.005 to the total amount of the raw materials.
It is preferably 0.05% by weight.

The glass transition temperature of polyester resin is 3
The temperature is preferably 5 to 100 ° C, and more preferably 50 to 90 ° C from the viewpoint of the balance between storage stability and toner fixability. If the glass transition temperature is lower than 35 ° C., the toner tends to cause blocking (a phenomenon in which toner particles aggregate and agglomerate) during storage or in a developing machine. On the other hand, when the glass transition temperature exceeds 100 ° C,
A large amount of heat energy tends to be required for fixing the toner. The said polyester resin is used individually or in combination of 2 or more types.

Examples of the polymerizable vinyl-based monomer used to obtain the vinyl-based polymer include styrene and styrene derivatives (α-methylstyrene, vinyltoluene, p
-T-butylstyrene, etc.), alkyl acrylate (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate,
Pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, etc.), alkyl methacrylate (methyl methacrylate, ethyl methacrylate, propyl methacrylate) , Butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate,
Dodecyl methacrylate). The polymerizable vinyl monomers are used alone or in combination of two or more.

Further, the above polymerizable vinyl-based monomer may be used in combination with other vinyl-based monomers (described later) other than these. The amount of the polymerizable vinyl-based monomer used is preferably 50% by weight or more, and more preferably 70% by weight or more, based on all the monomers.

Other vinyl monomers include, for example, 1
Vinyl monomers having one vinyl group in the molecule, for example, acrylic acid, methacrylic acid, acrylic acid derivatives other than alkyl acrylate (glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, acrylic acid Butoxyethyl, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, Benzyl acrylate, cyclohexyl acrylate,
Tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, N-vinyl-2-pyrrolidone acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy acrylate -3-Phenyloxypropyl, glycidyl acrylate, acrylonitrile, acrylamide, N-methylol acrylamide, diacetone acrylamide, etc.), methacrylic acid derivatives other than methacrylic acid alkyl esters (glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate), Butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxymethacrylate Ethylene glycol, butoxytriethylene glycol methacrylate, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, methacrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, methacrylonitrile, methacrylamide, N-methylolmethacrylamide, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxy methacrylate Butyl, methacrylic acid 2-hydroxy-
3-phenyloxypropyl, vinyl pyridine, etc. are mentioned. The other vinyl-based monomers are used alone or in combination of two or more.

Further, a monomer having two or more vinyl groups in one molecule may be used in combination, which is used as a crosslinking agent. As the monomer having two or more vinyl groups in one molecule, a monomer having two vinyl groups in one molecule is preferable from the viewpoint of stability such as fixing strength and offset resistance. Examples of such a monomer include divinylbenzene, a reaction product of glycol with methacrylic acid or acrylic acid (ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3- Butylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,
5-pentanediol diacrylate, 1,5-pentanediol dimethacrylate, etc.). The amount of these monomers used is preferably 20% by weight or less based on all the monomers.

As the vinyl-based polymer, styrene is contained in an amount of 50% by weight based on all monomers in terms of the balance of various properties.
A polymer obtained by using any of the above alkyl acrylates and alkyl methacrylates or a mixture thereof in a total amount of 50% by weight or more based on the remaining monomers is preferable.

As the method for polymerizing the vinyl-based monomer,
For example, known polymerization methods such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a seed polymerization method, and a bulk polymerization method can be used. Solution polymerization method, a solution containing a vinyl-based monomer and a polymerization initiator is added dropwise to a good solvent such as xylene,
This is a method in which a polymerization reaction is carried out by heating, and after the polymerization, a polymer can be obtained by putting the reaction solution in a poor solvent or removing the solvent from the reaction solution. The suspension polymerization method is a method in which a mixture of a vinyl monomer and a polymerization initiator is added to a solution containing a dispersant, the mixture is dispersed, and the polymerization reaction is performed by raising the temperature. Examples of the dispersant include an organic dispersant and an inorganic dispersant.Examples of the organic dispersant include polyvinyl alcohol, methylcellulose, polyvinylpyrrolidone, and sodium polyacrylate.Examples of the inorganic dispersant include calcium phosphate. , Calcium carbonate and the like.

In the emulsion polymerization method, a vinyl monomer is added to an aqueous solution containing a surfactant and a polymerization initiator, and a micelle structure of the vinyl monomer and the surfactant is formed to form a vinyl system in the aqueous solution. This is a method in which a monomer is dispersed and a polymerization reaction is carried out. In the dispersion polymerization method, a vinyl monomer and a polymerization initiator are placed in a mixed solution of water and alcohol, and the vinyl monomer is uniformly dissolved in the mixed solution, and then a polymerization reaction is performed. This is a method of precipitating and dispersing from a solution. In the seed polymerization method, seed particles are synthesized by a dispersion polymerization method or the like, the seed particles and a dispersant are added to a solvent, and after dispersion, a vinyl monomer and a polymerization initiator are added, and the mixture is heated under stirring. Thereby, the seed particles are sufficiently swollen with a vinyl monomer, a polymerization inhibitor is added, a dispersant is added if necessary, and the mixture is heated under stirring, whereby the vinyl monomer is added. This is a method of polymerizing a monomer. The bulk polymerization method is a method in which a vinyl monomer and a polymerization initiator are mixed and heated to cause a polymerization reaction.

Weight average molecular weight (Mw) of vinyl polymer
Is preferably 2,500 to 150,000, and more preferably 3,000 to 45,000. If the weight average molecular weight is less than 2,500, the toner tends to be crushed at the time of printing, resulting in 150,000.
If it exceeds, the fixability tends to decrease, and the color tone reproducibility tends to deteriorate. The weight average molecular weight is a value measured by gel permeation chromatography and calculated in terms of standard polystyrene.

The glass transition temperature of the vinyl polymer is preferably 35 to 100 ° C., and 50 to 90 ° C.
C. is more preferable. Glass transition temperature is 35 ℃
When the amount is less than the range, the toner tends to cause blocking (a phenomenon in which toner particles aggregate and agglomerate) during storage or in a developing machine. On the other hand, when the glass transition temperature exceeds 100 ° C., a large amount of heat energy tends to be required for fixing the toner. The above vinyl polymers are used alone or in combination of two or more.

The binder resin is preferably a resin composed of only a polyester resin or a resin composed of only a vinyl polymer from the viewpoint that the coloring of the resin itself is suppressed and the coloring with a coloring agent is carried out efficiently. It may be a mixture obtained by adding another resin to the vinyl polymer. As other resins, for example, amide resin, urethane resin, urea resin, epoxy resin, silicone resin, xylene resin,
Diene resin, styrene resin (however, compound not included in the above-mentioned vinyl polymer), acrylic resin (however, compound not included in the above-mentioned vinyl polymer), styrene-acryl resin (however, the above-mentioned vinyl Compounds not included in the polymer), phenolic resins, terpene resins, coumarin resins, amide imide resins, butyral resins, urethane resins, ethylene / vinyl acetate resins, and the like.

Examples of the amide resin include polymerizing caprolactam, dibasic acids (terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid, etc.) and diamines (ethylenediamine, diamino acid). It can be obtained by condensation polymerization of ethyl ether, 1,4-diaminobenzene, 1,4-diaminobutane and the like). The urethane resin is obtained, for example, by subjecting diisocyanates (p-phenylene diisocyanate, p-xylene diisocyanate, 1,4-tetramethylene diisocyanate, etc.) and glycols (ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, etc.) to an addition reaction. be able to.

Urea resins include, for example, diisocyanates (p-phenylene diisocyanate, p-xylene diisocyanate, 1,4-tetramethylene diisocyanate, etc.) and diamines (ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, 1, 4-diaminobutane etc.) can be obtained according to a conventional method. Epoxy resins include, for example, amines (ethylamine, butylamine, etc.), acrylic acid or methacrylic acid derivatives (acrylonitrile, methacrylonitrile, acrylamide, etc.), vinyl ethers (vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc.). , Vinyl ketones (vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.),
It can be obtained from N-vinyl compounds (N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like), vinylnaphthalene and the like according to a conventional method.

The blending amount of the above other resin is preferably 50% by weight or less based on the total amount of the binder resin. On the other hand, the compounding amount of the other resin is preferably 30% by weight or less based on all components (hereinafter referred to as toner components) added to the organic solvent to obtain a toner mother liquor.

The amount of the binder resin compounded is from the viewpoint of the balance between the binding force of the toner image to the support and the hiding power of the toner image.
It is preferably 60 to 95% by weight, more preferably 80 to 95% by weight, based on the toner component, and 8
More preferably, it is 5 to 90% by weight. If the blending amount is less than 60% by weight, the binding force of the toner image to the support becomes weak, and when the support of the toner image is bent or rubbed, the toner image is lost and information is easily lost. Tends to become. On the other hand, if it exceeds 95% by weight, the hiding power of the toner image tends to be insufficient and the print quality tends to be poor.

The colorant is variously selected depending on whether the toner to be obtained is a black toner or a color toner, and various organic pigments, inorganic pigments and dyes can be used. Examples of the colorant used for obtaining the black toner include carbon black, acetylene black, iron black, aniline black, cyanine black, and the like, among which carbon black is preferable. Examples of the colorant used for obtaining the color toner include a yellow colorant, a red colorant, a blue colorant, an orange colorant, a purple colorant, and a green colorant.

Examples of yellow colorants include Pigment Yellow (CI21105) and Naphthol Yellow S.
(CI10316), Hansa Yellow 10G (CI11
710), Hansa Yellow 5G (CI11660), Hansa Yellow G (CI11680), Hansa Yellow R
(CI12710), Pigment Yellow L (CI12
720), benzidine yellow G (CI21095),
Permanent Yellow NCG (CI20040), Vulcan Fast Yellow 5G (CI21220), Quinoline Yellow (CI47005), Permanent Yellow FGL (CI11767), Permanent Yellow H
R (CI21108) and the like.

Examples of red colorants include Pigment Red 122 (CI73915), Permanent Red 4R (CI12070), Para Red (CI1212).
0), Brilliant Fast Scarlet (CI123
15), Brilliant Carmine BS (CI1235
1), Permanent Red F4R (CI12335),
Vulcan Fast Rubin B (CI12320), Light Fast Red Toner B (CI12450), Lake Red C (CI15585: 1), Brilliant Carmine 6B (CI15850: 1), Rhodamine Lake B (CI45170: 2) and the like.

Examples of blue colorants include cobalt blue (CI77346) and alkali blue lake (CI
42750: 1), Victoria Blue Lake (CI44
045: 2), metal-free phthalocyanine blue (CI74
100), phthalocyanine blue (CI74160),
Fast Sky Blue (CI74180: 1) and the like. Examples of the orange colorant include permanent orange (CI12075), Vulcan fast orange GG (CI21165), and indanthrene brilliant orange RG (CI59300). Examples of purple colorants include First Violet B
(CI12321), methyl violet lake (CI
42535) and the like.

Examples of green colorants include Pigment Green B (CI10006), Acid Green Lake, Phthalocyanine Green (CI74260) and the like. The coloring agents are used alone or in combination of two or more. From the viewpoint of the balance between the hiding power and the fixing power of the toner, the amount of the colorant blended is preferably 0.1 to 15% by weight with respect to the toner component, and 1 to 1
It is more preferably 0% by weight, further preferably 3 to 5% by weight. If the content of the colorant is less than 0.1% by weight, the hiding power tends to be insufficient and poor printing quality tends to be obtained, and if it exceeds 15% by weight, the fixing power tends to decrease.

The organic solvent used in the toner mother liquor is not particularly limited as long as it can dissolve the binder resin. For example, hydrocarbons (toluene, xylene, hexane, etc.), halogenated hydrocarbons ( Methylene chloride, chloroform, dichloroethane, dichloroethylene, etc.), alcohol or ether (ethanol, butanol, benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether, tetrahydrofuran, tetrahydropyran, etc.), ester (methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, etc.) ), A ketone or an acetal (acetone, methyl ethyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, etc.) and the like.

Various additives may be added to the organic solvent in addition to the binder resin and the colorant, depending on the intended use of the toner to be obtained. As the additive, for example,
Examples include a magnetic or magnetizable material, an anti-offset agent, a positive or negative charge control agent, and silica powder. A magnetic or magnetizable material is added to obtain a toner for developing an electrostatic image having magnetism, and examples of such a material include oxides of iron, cobalt, nickel and the like (hematite, magnetite, etc.). . The magnetic or magnetizable material is used alone or in combination of two or more.

The blending amount of the magnetic or magnetizable material is appropriately selected depending on whether the toner to be obtained is a magnetic toner or a non-magnetic toner. In the case of a non-magnetic toner, toner scattering is suppressed. In view of this, the content is preferably 0.5 to 5% by weight, more preferably 1 to 4% by weight, and further preferably 2 to 3% by weight based on the toner component. If the blending amount is less than 0.5% by weight, the effect of suppressing toner scattering tends to be hardly obtained, and if it exceeds 5% by weight, the fixing property tends to decrease.

Examples of the anti-offset agent include lower alcohol esters of fatty acids (butyl stearate, propyl stearate, etc.), higher alcohol esters of fatty acids (casta wax, diamond wax, etc.), higher alcohol esters (palm acetyl, Hoechst wax E). , Hoechst wax OP, carnauba wax, etc.), alkylene bis fatty acid amide compounds (bisamide blast flow, amides 6L, 7S, 6H, Hoechst wax C, etc.), olefin monomers (ethylene, propylene, butene, hexene, heptene, Octene, nonene, decene, 3-methyl-1-butene, 3-methyl-2
-Pentene, 3-propyl-5-methyl-2-hexene, etc.) or a copolymer of these olefin monomers with acrylic acid, methacrylic acid, butyl acetate, etc. Among these offset preventing agents, polypropylene is preferable from the viewpoint that it can meet various conditions of electrophotography. The above offset preventing agents are used alone or in combination of two or more kinds.

From the viewpoint of the balance between the offset prevention effect and the powder fluidity of the toner, the amount of the above-mentioned offset inhibitor to be blended is preferably 0.1 to 10% by weight, and preferably 0.1 to 10% by weight. More preferably, it is 5% by weight. If the blending amount is less than 0.1% by weight, a sufficient offset preventing effect tends to be difficult to be exhibited, and if it exceeds 10% by weight, the powder fluidity of the toner is lowered and the developability is deteriorated. There is a tendency that the transparency of the toner is lowered and it is difficult to obtain a desired color tone.

Examples of positively chargeable charge control agents include, for example:
Nigrosine dyes of azine compounds (Bontron 03 (trade name of Orient Chemical Industry Co., Ltd.), etc.), quaternary ammonium salts (Bontron P-51 (trade name of Orient Chemical Industry Co., Ltd.), etc.), quaternary ammonium salts Molybdenum complex (T
P-302 (trade name of Hodogaya Chemical Co., Ltd.), TP-41
5 (trade name of Hodogaya Chemical Co., Ltd.), quaternary ammonium salt (Copy Charge PSY VP)
2038 (trade name of Hoechst), triphenylmethane derivative (Copy Blue)
PR (trade name of Hoechst), LRA-90
1 (trade name of Nippon Carlit Co., Ltd.) and the like. Among these positively chargeable charge control agents, the quaternary ammonium salt molybdenum complex is preferable from the viewpoint of excellent charge stability.

Examples of the negatively chargeable charge control agent include, for example,
Metal-containing azo dye (Bontron S-34 (trade name of Orient Chemical Industry Co., Ltd.), etc.), oxynaphthoic acid metal complex (E-82 (trade name of Orient Chemical Industry Co., Ltd.), etc.), salicylic acid metal complex ( E-84 (Orient Chemical Industry
(Trade name) etc.), phenolic condensate (E-89 (trade name of Orient Chemical Industry Co., Ltd.) etc.), quaternary ammonium salt (Copy Charge NEG VP
2036, Copy Charge NX VP434 (both are trade names of Hoechst, etc.), boron complex (LR-14)
7 (trade name of Nippon Carlit Co., Ltd.) and the like. Among these negatively chargeable charge control agents, the boron complex is preferable from the viewpoint of excellent charge stability. These positively or negatively chargeable charge control agents are used alone or in combination of two or more. When two or more types are combined, a combination of positively chargeable charge control agents, a negatively chargeable charge control agent Any combination of the combination of the positive charge control agent and the negative charge control agent may be used.

These charge control agents are used within a range that does not impair the color tone of the toner image to be fixed, and their blending amount should be 0.5 to 5.0% by weight based on the toner components. Is preferable, 0.5 to 3% by weight is more preferable, and 1 to 3% by weight is further preferable. If the blending amount is less than 0.5% by weight, the charging effect tends to be difficult to obtain, while the blending amount is 5% by weight.
When the value exceeds the above, the charge amount becomes high from the beginning, and therefore the print density is low, the transferability from the photoconductor to the toner support is poor, and the cleaning property of the transfer residual toner adhering to the photoconductor is poor. Problems tend to occur.

As the silica powder, known ones can be used. Examples of such silica powder include Aerosil R972, R974, Silica D-17, T-805, R-812, and RA.
200, HRX-C (both are trade names of Nippon Aerosil Co., Ltd.), Talanox 500 (trade name of Tarco), Cab
-O-Sil M-5, MS-7, MS-75, HS-
5, EH-5, S-17, TS-72 (all are trade names of Cabot Co.). Among these silica powders, RA200 is preferable because of its excellent fluidity and charge stability. The silica powder is used alone or in combination of two or more kinds. When these silica powders are blended, the blending amount is preferably 0.5 to 3% by weight with respect to the toner component,
More preferably, it is 5 to 1% by weight. If the blending amount is less than 0.5% by weight, the effect of improving the fluidity tends to be hardly obtained, and if it exceeds 3% by weight,
The fixability of the toner tends to decrease.

A toner mother liquor is prepared by adding the above-mentioned binder resin and colorant, and (if necessary) additives to an organic solvent. The concentration of the solid content in the toner mother liquor, that is, the ratio (%) of the weight of all the components other than the organic solvent in the toner mother liquor to the weight of the toner mother liquor, is a factor in the balance between the toner granulability and the toner yield. Therefore, it is preferably 25 to 55% by weight, more preferably 30 to 50% by weight, and further preferably 35 to 45% by weight.
If the concentration is less than 25% by weight, the yield of the toner tends to decrease, and if it exceeds 55% by weight, the granulation of the toner tends to be inferior and the particle size distribution of the toner tends to widen. When preparing the toner mother liquor, a high-viscosity agitator Haydon Suriwan Motor 600G (trade name, manufactured by Shinto Kagaku Co., Ltd.) is used, and the peripheral speed of rotation of the rotor is 0.75 to 1.
It is preferable to stir under stirring conditions of 7 m / sec.

The viscosity of the toner mother liquor is E at a shear rate of 76.8 m / s at 25 ° C. from the point of dispersion of the toner mother liquor in the aqueous solution.
The value measured by a viscometer is preferably 1 to 30 mPa · s, more preferably 20 to 30 mPa · s. If the viscosity is less than 1 mPa · s or more than 30 mPa · s, the dispersion tends to be insufficient and the toner yield tends to decrease.

The toner mother liquor is mixed with an aqueous solution containing a surfactant and an inorganic dispersant. As the surfactant, known surfactants can be used, and examples thereof include anionic, cationic and nonionic surfactants.
Examples of the anionic surfactant include sodium alkylbenzenesulfonate, sodium α-olefin sulfonate, sodium alkylsulfonate, and sodium alkyldiphenyletherdisulfonate. Examples of the cation-type surfactant include alkylamine salts (stearylamine hydrochloride, dioleylamine sulfate, etc.), quaternary alkylammonium salts (stearyltrimethylammonium chloride, etc.), amine oxides (lauryldimethylamine oxide, etc.). And so on. Nonionic surfactants include, for example, polyoxyethylene alkyl ethers (such as polyoxyethylene lauryl ether), polyoxyethylene alkyl aryl ethers (such as polyoxyethylene nonyl phenyl ether), sorbitan fatty acid esters (such as sorbitan monolaurate) ).

Among these surfactants, anionic type surfactants are preferable from the viewpoint of excellent stability of oil droplets,
In view of the stability and resolution of the toner when used in combination with an inorganic dispersant, sodium alkylbenzenesulfonate is particularly preferred. An example of sodium alkylbenzenesulfonate is sodium dodecylbenzenesulfonate. These surfactants are used alone or in combination of two or more. The blending amount of these surfactants is 1 × 10 ^{−5 to} 0.1 with respect to the toner mother liquor from the viewpoint of the balance between the particle size distribution of the toner and the cleaning power.
It is preferably in the weight%. This amount is 1 × 10 ^-5
If the amount is less than 0.1% by weight, the particle size distribution of the toner tends to be wide, and if it exceeds 0.1% by weight, the detergency tends to decrease. After adding the toner mother liquor, these surfactants may be further added to the aqueous solution. The toner may be added during the dispersion of the toner particles or after the end of the dispersion.

Examples of the inorganic dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, silica powder and the like. Among these inorganic dispersants, tricalcium phosphate and hydroxyapatite are preferable in terms of granulation properties, stability thereof, and extremely little adverse effect on the properties of the obtained toner. The average particle size of the inorganic dispersant is preferably from 0.1 to 2 μm. When the average particle diameter is less than 0.1 μm, the particle diameter of the obtained toner tends to be too small,
When the ratio exceeds, the particle diameter of the obtained toner tends to be too large.

The average particle size referred to here is a photon correlation method by laser scattering, a submicron particle analyzer analyzer (SUB-MICRON PARTICLE ANALYZER, model N4MD, a collector electronic device (COULTER).
ELECTRONICS)) and dispersed in a 10 ppm sodium dodecylbenzene sulfonate solution, this machine is a particle size measurement system, SDP INTENSITY RESULTS.
It is the average particle size measured by setting to (MODE). Dispersion in a 10 ppm sodium dodecylbenzenesulfonate solution was carried out for 1 minute using an ultrasonic disperser having a frequency of 40 kHz.

The concentration of the inorganic dispersant in the aqueous solution containing the surfactant and the inorganic dispersant is appropriately determined depending on the particle size when the toner mother liquor is granulated in the aqueous solution. From the viewpoint of yield balance, 1 to 10
It is preferably wt%, more preferably 2 to 10 wt%, even more preferably 3 to 10 wt%. If this concentration is less than 1% by weight, the chargeability of the toner particles tends to decrease, and if it exceeds 10% by weight, unnecessary fine particles are generated and the target particles are obtained in high yield. Tends to be difficult. The concentration of the inorganic dispersant is preferably 1 to 16% by weight based on the toner mother liquor from the viewpoint of the balance between the granulation of toner particles and the yield. If this concentration is 1% by weight, granulation is difficult to be sufficiently performed, and aggregates tend to be generated, and 16% by weight
If it exceeds, unnecessary fine particles are generated, and it tends to be difficult to obtain target particles in high yield.

The toner mother liquor is mixed with an aqueous solution containing a surfactant and an inorganic dispersant. The blending amount of the toner mother liquor is preferably 10 to 50% by weight, based on the total amount of the toner mother liquor and the aqueous solution, from the viewpoint of the yield of toner particles and the avoidance of oil droplet coalescence during granulation. %, More preferably 20 to 30% by weight. When the amount is less than 10% by weight, the particle size distribution of the toner particles is widened, and the yield of the target toner particles tends to be relatively low. There is a tendency that granulation cannot be achieved due to drop coalescence.

When the toner mother liquor and the aqueous solution are mixed,
It is preferable to stir the mixture under high-speed shearing using an apparatus equipped with a high-speed shearing mechanism or the like. Various types of high-speed dispersers can be used as devices provided with the high-speed shearing mechanism, and examples of the high-speed dispersers include homogenizers. Here, the homogenizer means that substances that are incompatible with each other pass through a narrow gap between the casing (fixing plate) and the rotor that rotates at high speed, whereby a substance that is incompatible with the liquid is converted into fine particles in a certain liquid. Refers to a device for dispersing in In the present invention, the incompatible substances correspond to an aqueous solution containing an inorganic dispersant and a surfactant and a toner mother liquor.
Such homogenizers include, for example, TK homomixer, line flow homomixer (both are trade names of Tokushu Kika Kogyo Co., Ltd.), Silverson homogenizer (Silverson Corporation trade name), Polytron homogenizer (KINEMATICA) AG Company name). When stirring using a homogenizer, the peripheral speed of the rotor blades is preferably 8 m / sec or more. If the peripheral speed is less than 8 m / sec, the fine particles tend to be insufficient.

By the above stirring operation, oil droplets of the toner mother liquor are granulated in the aqueous solution, and the volume average particle diameter thereof is 4 to 1
It is preferably 0 μm. This volume average particle diameter is 4
If it is less than μm, the fluidity tends to deteriorate and the image quality tends to deteriorate, and if it exceeds 10 μm, the melting and mixing properties are insufficient when the three primary colors are mixed to develop an intermediate color during the production of a full-color toner. Therefore, it is difficult to produce an intermediate color, and it is difficult to increase the resolution. Furthermore, from the viewpoint of charge stability of the obtained toner and fluidity of the toner particles,
The amount of the fine particles having a particle size of 3 μm or less is set to 7% by volume or less based on the total amount of the obtained toner particles, and the amount of the coarse particles having a particle size exceeding 20 μm is minimized (preferably to 0% by volume). Is preferred. In addition, these particle diameters are measured by using a counter-TA-II (trade name of Nikkaki Co., Ltd.).

After granulating the toner particles, the organic solvent and water are removed to obtain a toner. The operation of removing the organic solvent may be, for example, vaporizing the organic solvent at room temperature and atmospheric pressure, but in order to shorten the time required to remove the organic solvent, the temperature is lower than the boiling point of the organic solvent used, and 80 ° C difference from boiling point
It is set within the following range, and the degree of vacuum is 146 × 10 ² to 4
It is preferable to vaporize at 80 × 10 ² Pa.

After removing the organic solvent, the pH of the aqueous solution is from 1 to 10 from the viewpoint of improving the characteristics by making the composition of the toner original.
It is preferable to add an acid (hydrochloric acid, sulfuric acid, formic acid, acetic acid, etc.) to the aqueous solution so as to obtain 3, and stir the aqueous solution to remove the inorganic dispersant remaining on the surfaces of the toner particles. To remove water from an aqueous solution containing toner, for example,
A method in which the aqueous solution is dehydrated using a centrifuge and dried at 40 to 50 ° C using a vacuum dryer can be used. The residual water content of the toner is preferably 0.3% by weight or less based on the total amount of the obtained toner.

The obtained toner can be used for electrostatic image development. In order to further improve physical properties such as fluidity and chargeability, the toner contains fine particles (fine silica powder, vinyl-based polymer or copolymer, zinc stearate, aluminum oxide, etc.) as external additives. , Titanium oxide, etc.) may be added to and mixed with the toner so that these fine particles are attached to the surface of the toner particles. The amount of these external additives added is 0.05 to 5% by weight in total with respect to the toner, from the viewpoint of the balance between charge stability and fluidity of the toner.
And preferably 0.2 to 0.5% by weight.

The obtained toner can be mixed with a carrier to form a developer. The type of carrier is not particularly limited, and known materials such as iron oxide powder, various ferrites, and magnetite can be used. The mixing ratio of the toner and the carrier is not particularly limited, and a known mixing ratio can be used. Usually, the toner is used in an amount of 1 to 10% by weight based on the developer. Each step of electrophotography when using the toner and developer obtained by the production method of the present invention, that is,
As the charging step, the exposure step, the transfer step, the fixing step, the cleaning step, and the charge removal step, any of the known steps can be used.

[0062]

The present invention will be described in detail below with reference to examples. In addition, in Tables 1-6, the unit of the compounding quantity of a raw material is all a weight part. Production Example 1 Production of Polyester Resin The acid component and the alcohol component shown in Table 1 were charged into a reaction vessel, and the temperature was gradually increased while blowing nitrogen gas.
The condensation reaction was allowed to proceed at 0 ° C. for 5 hours, and then the reaction was completed at 230 ° C. to obtain polyester resins (R-1) to (R-5). The glass transition temperature of the obtained resin is also shown in Table 1.

[0063]

[Table 1]

Production Example 2 Production of Vinyl Polymer 300 g of xylene as a solvent was charged in a pressure reaction vessel,
The temperature was raised to 130 ° C., and 100 g of the polymerizable vinyl-based monomer shown in Table 2 and a polymerization initiator were added dropwise to this xylene over 3 hours. After advancing the reaction for 8 hours to complete the reaction, about 90% by weight of xylene was removed by distillation under reduced pressure, and the product was taken out from the reaction vessel. Then, the solvent removal was continued for 12 hours at a temperature of 180 ° C. under a reduced pressure of 133.3 Pa or less with a vacuum dryer,
Vinyl polymers (R-6) to (R-10) were obtained. Table 2
The glass transition temperature and molecular weight (weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight dispersity (Mw / Mn)) of the obtained vinyl polymer are also shown in Table 1. The weight average molecular weight and the number average molecular weight in Table 2 are values measured by gel permeation chromatography and expressed in terms of standard polystyrene.

[0065]

[Table 2]

Examples 1 to 6 Using a ball mill, the binder resin, colorant (pigment), organic solvent and additive shown in Table 3 were stirred until the pigment particles became submicron, to prepare a toner mother liquor.

[0067]

[Table 3]

Using a homogenizer, the obtained toner mother liquor was added to an aqueous solution containing an inorganic dispersant (hydroxyapatite) and a surfactant (sodium dodecylbenzenesulfonate) under the conditions shown in Table 4, and granulated. The toner mother liquor was dispersed in the aqueous solution by stirring so that the peripheral speed of the rotor was 6 to 12 m / sec and the temperature was 35 ° C. so that the average particle diameter of the oil droplets was 5 to 9 μm. The 5% by weight aqueous solution of hydroxyapatite was 391 parts by weight of trisodium phosphate dodecahydrate and 13% by weight of sodium hydroxide.
An aqueous solution obtained by dissolving 220 parts by weight of calcium chloride in 1100 parts by weight of water was added dropwise to an aqueous solution in which 1300 parts by weight of water was dissolved, and the mixture was obtained by stirring at 20 to 30 ° C. After the dispersion was completed, the organic solvent was distilled off under normal pressure or reduced pressure under the temperature conditions that were lower than the boiling point of the solvent and the difference from the boiling point was 80 ° C. or less. Specifically, when toluene is used as the organic solvent, the temperature is 60 to 75 ° C. and the degree of vacuum is 237 ×.
10 ^{2 to} 384 × 10 ² Pa, the temperature is 20 to 30 ° C. when methylene chloride is used, and the temperature is 50 to 50 when a mixed liquid of methyl ethyl ketone and toluene is used under normal pressure.
The temperature was 70 ° C. and the degree of vacuum was 237 × 10 ^{2 to} 384 × 10 ² Pa.

After removing the organic solvent, the aqueous solution containing the toner was cooled, 35% concentrated hydrochloric acid was added to the aqueous solution until the pH reached 2, and the mixture was stirred, and the toner was washed with water, whereby the inorganic dispersant was washed away. The remaining aqueous solution was dried and classified to obtain a solid toner having a volume average particle size in the range of 4 to 8 μm. Toner obtained when toluene is used as the organic solvent
The residual amount of toluene was measured by gas chromatography and was 0.01 to 0.4% by weight based on the toner. The toner yields of Examples 1 to 6 are 80 to 90.
% By weight. Micro compression tester (manufactured by Shimadzu Corporation,
MCT type) was used to determine the mechanical strength of the obtained toner according to the above formula (I), and the results are shown in Table 4. The toner external additives shown in Table 4 were further added to 100 parts by weight of the obtained toner, and stirred and mixed with a Henschel mixer to obtain a toner containing the external additives.

[0070]

[Table 4]

Comparative Example 1 The binder resin, colorant and additive of Example 2 in Table 3 were premixed with a Henschel mixer and then melt-kneaded with a biaxial kneader. Next, this kneaded product was cooled and pulverized by a pin mill and a jet mill to obtain an irregular toner having an average particle diameter of 8 μm. The mechanical strength of the obtained amorphous toner was determined as described above and found to be 3.85 kgf / mm ² .
The toner yield was low at 60% by weight. further,
Aerosil R972 (Nippon Aerosil)
0.2% by weight based on the amount of toner.
The toner was mixed with a Henschel mixer to obtain a toner containing an external additive.

Comparative Example 2 Example 4 was repeated, except that the dispersion medium in Example 4 was changed to an aqueous solution containing 3% by weight of polyvinyl alcohol (Denka Poval W-24 (trade name of Denki Kagaku Kogyo KK)).
By performing the same operation as above, a spherical toner having an average particle diameter of 6 μm was obtained. The mechanical strength of the obtained spherical toner was determined as described above and was found to be 0.22 kgf / mm ² . Further, the yield of the toner was as low as 20% by weight. Further, Aerosil R972 (trade name of Nippon Aerosil Co., Ltd.) was added to this toner in an amount of 0.1% by weight based on the amount of the toner, and mixed by a Henschel mixer to obtain a toner containing an external additive.

Examples 7 to 12 Toners were manufactured according to the above-mentioned "Examples 1 to 6". However, the composition of the binder resin, the colorant (pigment), the organic solvent and the additive was as shown in Table 5, and the dispersion condition and the composition of the external additive were as shown in Table 6. The toner yields of Examples 7 to 12 were 80 to 90% by weight.

[0074]

[Table 5]

[0075]

[Table 6]

Comparative Example 3 According to Comparative Example 1 except that the binder resin, colorant and additive of Example 8 in Table 5 were used, an irregular toner having an average particle size of 8 μm was obtained. The mechanical strength of the obtained amorphous toner was determined as described above, and the result was 3.65 kgf / mm ² . The toner yield was low at 60% by weight. Further, 0.2% by weight of Aerosil R972 (trade name of Nippon Aerosil Co., Ltd.) was added to this toner and mixed by a Henschel mixer to obtain a toner containing an external additive.

Comparative Example 4 Example 9 was repeated except that the dispersion medium was changed to an aqueous solution containing 3% by weight of polyvinyl alcohol (Denka Poval W-24 (trade name of Denki Kagaku Kogyo KK)) in Example 9 of Table 6.
By performing the same operation as above, a spherical toner having an average particle diameter of 6 μm was obtained. The mechanical strength of the obtained spherical toner was determined as described above, and it was 0.18 kgf / mm ² . Further, the yield of the toner was as low as 28% by weight. Further, 0.3% by weight of Aerosil R972 (trade name of Nippon Aerosil Co., Ltd.) was added to this toner and mixed by a Henschel mixer to obtain a toner containing an external additive.

Evaluation 95% by weight of a copper-zinc ferrite carrier coated with an acrylic resin-modified silicone resin and having an average particle diameter of 40 μm
5% by weight of the toner obtained in each of Examples 1 to 12 and Comparative Examples 1 to 4 was added to obtain a developer. Using this developer, a full color printer QMS Color Scriput Laser1000 (trade name of QMS Co.) capable of printing 8 sheets of A4 size paper per minute is used.
The pages were printed continuously. However, the number of printed pages is 10,000 in Comparative Examples 1 and 3, and the number of printed pages is 2 in Comparative Examples 2 and 4.
It was set to 000. The printed matter obtained is evaluated according to the following criteria,
The results are shown in Tables 7 and 8.

(A) Reproducibility of color tone: It was printed on OHP (overhead projector) paper, and the reproducibility of a color image was examined by OHP and evaluated according to the following criteria. Good: A chromatic color is developed, and an intermediate color is also developed. Inferior: chromatic color does not appear. (B) Image density, fog and resolution Image density and fog were measured using a Macbeth reflection densitometer RD514 (A division kollmorgen Corp. trade name). For the resolution, the image of the Electrophotographic Society of Japan Chart No. 5-2 was copied, and the image was magnified 10 times to find how many lines of equal width and even intervals (line pair / mm) per 1 mm were resolved. It was visually determined whether or not there is any.

(C) Toner scattering The presence or absence of toner scattering was visually determined. (D) Cleanability The transfer residual toner on the photoreceptor that has passed through the cleaning process is transferred to a blank sheet using Scotch tape (trade name of Sumitomo 3M Limited).
It was measured with a Macbeth reflection densitometer RD514, and the difference from the blank was examined. Those with a difference of 0.04 or less were evaluated as "good", and those with a difference of more than 0.04 were evaluated as "poor".

[0081]

[Table 7]

[0082]

[Table 8]

As is clear from Table 7, when the toner obtained in Comparative Example 1 was used, the color tone reproducibility was poor even at the initial stage, a little fog was observed, and the resolution was a little low. Even after printing 10,000 pages, the color reproducibility was poor, the image density and the resolution were significantly reduced, and fog and toner scattering were observed. Furthermore, when the toner obtained in Comparative Example 2 was used, the color tone reproducibility was inferior even at the initial stage (light did not pass through), some fog was observed, toner scattering was also seen, and the resolution was slightly low. And, even if only 2,000 pages are printed, the color reproducibility is inferior (light is not transmitted),
The image density and resolution were greatly reduced, fogging and toner scattering were observed, and the cleaning property was also poor. On the other hand, when the toners obtained in Examples 1 to 6 were used, the color tone reproducibility and the cleaning property were good even after printing 30,000 pages, the resolution and the image density were high, and there was almost no fog. There was no scattering.

On the other hand, as is clear from Table 8, Comparative Example 3
When the toner obtained in 1. was used, the color tone reproducibility was poor even in the initial stage, a little fog was observed, and the resolution was a little low. Even after printing 10,000 pages, the color reproducibility was poor, the image density and the resolution were significantly reduced, and fog and toner scattering were observed. Furthermore, when the toner obtained in Comparative Example 4 is used, the color tone reproducibility is poor even in the initial stage, a little fog is observed, and toner scattering is also observed.
The resolution was a bit low. Even after printing 2,000 pages, the color tone reproducibility was poor, the image density and resolution were greatly reduced, fog and toner scattering were observed, and the cleanability was also poor. On the other hand, when the toners obtained in Examples 7 to 12 are used, the color tone reproducibility and the cleaning property are good even when 30,000 pages are printed, the resolution and the image density are high, and the fog hardly occurs. There was no scattering.

[0085]

The toner according to claim 1 has a color reproducibility,
It has excellent resolution and cleanability, high image density and little fog, and is suitable for developers. The toner according to claim 2 is
The toner has the effects of the first aspect, and further has excellent durability against agitation by a developing machine, and is suitable as a developer.
The toner according to claim 3 has the effect of the toner according to claim 2, and has a narrow particle size distribution, and is suitable as a developer. The toner according to claim 4 has the effect of the toner according to claim 2 or 3, and has excellent chargeability, and is suitable as a developer. The toner according to claim 5 has the effect of the toner according to any one of claims 2 to 4, and has a narrower particle size distribution, and is suitable for a developer. The developer according to claim 6 is excellent in color tone reproducibility, resolution and cleanability, has a high image density, has little fog, and is useful for developing an electrostatic image.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Okada 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (6)

[Claims] (1) Formula (I) (In the formula, P represents a 10% deformation load (kgf), and d represents a toner particle diameter (mm)).
Toner that is ^{3 to} 3.2 (kgf / mm ² ). 2. A method obtained by mixing a toner mother liquor containing a binder resin, a colorant and an organic solvent with an aqueous solution containing a surfactant and an inorganic dispersant, and then removing the organic solvent and water. 1. The toner according to 1. 3. The toner has a solid content of 25 to 5 in the mother liquor.
The toner according to claim 2, which is 5% by weight. 4. The concentration of the inorganic dispersant in the aqueous solution is 1 to 10.
The toner according to claim 2 or 3, wherein the toner is wt%. 5. The compounding amount of the toner mother liquor with respect to the total amount of the toner mother liquor and the aqueous solution is 10 to 50% by weight.
The toner according to any one of the above. 6. A developer containing the toner according to claim 1 and a carrier.