JP2000187352A - Electrostatic charge image developing toner and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an electrostatic charge image developing toner which is easily releasable and has a wide fixable temperature range. SOLUTION: The electrostatic charge image developing toner comprises colored particles obtained by aggregating and heat-fusing fine resin particles, fine releasing agent particles and fine colorant particles. The difference between the acid value of the fine releasing agent particles and that of the fine resin particles is greater than 10 and smaller than 20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image and a method for producing the same.

[0002]

2. Description of the Related Art In an example of electrophotography, a latent image carrier having a photosensitive layer (hereinafter, also referred to as a "photoconductor") is provided with a uniform electrostatic charge, and is then subjected to image exposure. An electrostatic latent image corresponding to the document is formed on the surface of the photoconductor, and the electrostatic latent image is developed by a developer to form a toner image. This toner image is transferred to a transfer material such as paper and then fixed by heating or pressing to form a copied image.

As toners used for such image formation, toners (polymerized toners) obtained by various fusing / associating methods are used instead of toners obtained by a conventional kneading / pulverizing method. For example, JP-A-60-220
358, JP-A-4-284664, etc.).

On the other hand, as a method for fixing a toner image, a heat roller fixing method, which has high thermal efficiency and is advantageous from the viewpoint of safety, is widely used. However, when such a heat roller fixing method is adopted, a part of the molten toner is transferred and adhered to the surface of the heat roller, and the transferred toner is transferred again to the next transfer paper to stain the image. Offset development is likely to occur. Therefore, the toner has a temperature range (hereinafter, referred to as a “fixable temperature range”) that has good releasability (offset prevention effect) and can perform fixing without causing an offset phenomenon. It is desirable to be wide.

[0005] As a means for preventing the occurrence of the offset phenomenon, a releasing agent (wax) is added to the toner to impart releasability to the toner itself. However, conventionally known polymerized toners containing a release agent have a problem that the release agent is uniformly present in the polymerized toner particles and the offset prevention effect of the release agent is not sufficiently exhibited. That is, in order to sufficiently exert the effect of the release agent, the release agent contained in the toner particles is preferably present near the surface of the toner particles, and the release agent is uniformly dispersed in the toner particles. In the existing state, it is difficult to impart effective releasability (offset prevention effect) to the toner.

[0006]

SUMMARY OF THE INVENTION The present invention has been made based on the above circumstances. SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image having a good releasability and a wide fixing temperature range. Another object of the present invention is to provide a method capable of producing a toner for developing an electrostatic image having good releasability and a wide fixable temperature range.

[0007]

The toner for developing an electrostatic image of the present invention comprises an electrostatic image composed of colored particles obtained by aggregating and thermally fusing resin fine particles, release agent fine particles and colorant fine particles. In the developing toner, when the acid value of the resin fine particles is A and the acid value of the release agent fine particles is B, a condition represented by the following formula 1 is satisfied.

[0008]

(Equation 1) 0 <BA ≦ 20

In the toner for developing an electrostatic image of the present invention, the following forms are preferred. (1) The resin fine particles are made of a thermoplastic copolymer containing at least one kind of acidic polar group selected from a carboxyl group, a sulfone group and a phospho group. (2) The release agent fine particles are composed of a release agent containing a carboxyl group. (3) The release agent fine particles are composed of at least one release agent selected from acid-modified low molecular weight polypropylene, acid-modified low molecular weight polyethylene and oxidized wax. (4) A dispersion in which fine particles of a release agent comprising at least one release agent selected from an acid-modified low-molecular-weight polypropylene, an acid-modified low-molecular-weight polyethylene, and an oxidized wax are dispersed in an aqueous phase, a dispersion of resin fine particles, and coloring. A resin particle, a releasing agent particle, and a coloring agent particle obtained by mixing and thermally fusing the resin particle, a releasing agent particle, and a coloring agent particle. (5) Resin fine particles formed by subjecting a monomer to granulation polymerization in a liquid phase in the presence of release agent fine particles, and the release agent fine particles and the colorant fine particles are obtained by coagulation and thermal fusion. It is composed of colored particles, and the acid value of the resin fine particles is A,
When the acid value of the release agent fine particles is B, the condition represented by the above formula 1 is satisfied.

The method for producing a toner for developing an electrostatic image of the present invention comprises a step of preparing colored particles by coagulating and thermally fusing resin fine particles, release agent fine particles and colorant fine particles. Wherein the acid value of the resin fine particles is A, and the acid value of the release agent fine particles is B,
It is characterized by satisfying the condition shown in the above equation (1).

The method for producing a toner for developing an electrostatic image according to the present invention is characterized in that the resin fine particles formed by subjecting a monomer to granulation polymerization in a liquid phase in the presence of a releasing agent fine particle; A process of preparing colored particles by aggregating and thermally fusing the developer fine particles and the colorant fine particles, wherein the acid value of the resin fine particles is A and the acid value of the release agent fine particles is B,
The following conditions are satisfied.

[0012]

(1) The dispersion stability of the fine particles in the liquid phase is as follows.
Depending on the acidic polar group (for example, a carboxyl group) present on the surface of the fine particles, the more acidic polar groups present on the surface of the fine particles, the better the dispersion stability. Therefore, by setting the acid value of the release agent fine particles higher than the acid value of the resin fine particles, the dispersion stability of the release agent fine particles in the liquid phase becomes larger than the dispersion stability of the resin fine particles. For this reason, when performing the aggregation treatment in the liquid phase in which the resin fine particles and the release agent fine particles are dispersed, the release agent fine particles that are aggregated first and subsequently aggregated are in the obtained toner particles. In the above, the material is localized near the surface, and as a result, the releasability effect is improved. (2) When the difference between the acid value (B) of the release agent fine particles and the acid value (A) of the resin fine particles is 20 or less, the release agent fine particles can be contained in the toner particles. If it exceeds 20, the amount of the release agent particles just attached to the surface of the toner particles increases, which adversely affects the charging of the toner particles.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. [Electrostatic Image Developing Toner] The electrostatic image developing toner of the present invention is a toner for developing an electrostatic image containing resin fine particles, release agent fine particles and colorant fine particles. ) And the acid value (A) of the resin fine particles (B−
A) is more than 0 and 20 or less, preferably 5 to 2
It is characterized by being 0.

When the acid value (B) of the release agent fine particles is lower than the acid value (A) of the resin fine particles, good release properties cannot be imparted to the toner for developing an electrostatic charge image. The temperature range where the toner can be fixed is narrowed. Further, even when the difference between the acid value (B) of the release agent fine particles and the acid value (A) of the resin fine particles exceeds 20, good releasability can be imparted to the electrostatic image developing toner. Therefore, the temperature range where the toner can be fixed is narrowed.

In the present invention, the term "acid value (B) of the release agent fine particles" means the water necessary for neutralizing the acid (acid polar group existing at the molecular end) contained in 1 g of the release agent fine particles. Refers to the number of milligrams of potassium oxide. The “acid value (A) of the fine resin particles” refers to the acid contained in 1 g of the fine resin particles (existing at the molecular end), which is calculated from the inflection point of the titration curve obtained by the following electric conductivity titration method. Acidic polar group)
Means the number of milligrams of potassium hydroxide required to neutralize

(Electrical Conductivity Titration Method) The electric conductivity titration method involves diluting a dispersion of resin fine particles to a solid content of 5%,
0.5N sodium hydroxide aqueous solution at intervals of 15 seconds
In this method, the titration curve is measured using the conductivity and the amount of the sodium hydroxide solution added dropwise, and the inflection point is determined from the titration curve.

<Resin Fine Particles> The acid value (A) of the fine resin particles constituting the toner for developing an electrostatic image of the present invention is preferably 2 or more from the viewpoint of dispersion stability as fine particles in a liquid phase. And more preferably 5 or more.

The glass transition point (Tg) of the fine resin particles constituting the toner for developing an electrostatic image of the present invention is -10 to 120 ° C.
And more preferably 0 to 9
It is in the range of 0 ° C.

The softening point (Ts) of the fine resin particles constituting the toner for developing an electrostatic image of the present invention is preferably in the range of 80 to 220 ° C.

The monomer composition used for preparing the resin fine particles has a glass transition point (Tg) and a softening point (Ts) within the above-mentioned range, and the structural unit having an acidic polar group is 0.1%. It is not particularly limited as long as it can constitute a thermoplastic copolymer contained in a proportion of up to 20% by weight.

The molecular weight of the resin fine particles constituting the toner for developing an electrostatic image of the present invention is expressed by weight average molecular weight (Mw).
Is preferably in the range of 2,000 to 1,000,000, more preferably 8,000 to 500,000.
It is in the range of 0. In addition, the molecular weight distribution of the resin fine particles is determined by the ratio (Mw) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
w / Mn), and the ratio (Mw / Mn) is 1.5
It is preferably in the range of 100 to 100, and more preferably in the range of 1.8 to 50.

As the polymerizable monomer for synthesizing the resin fine particles constituting the toner for developing an electrostatic image of the present invention, for example, a hydrophobic monomer and a monomer having an acidic polar group are used. A crosslinkable monomer is used if necessary.

(1) Hydrophobic monomer The "hydrophobic monomer" for synthesizing resin fine particles is not particularly limited, and a conventionally known monomer can be used. In addition, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics. Specifically, a monovinyl aromatic monomer,
(Meth) acrylic ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers and the like are preferably used. be able to.

The monovinyl aromatic monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-methoxystyrene,
Phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p- Styrene-based monomers such as n-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof.

Examples of (meth) acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, and methacrylic acid. Examples include ethyl, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl benzoate and the like. Examples of the vinyl ether-based monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-
Monoolefinic monomers such as pentene and 4-methyl-1-pentene are exemplified. Examples of the diolefin-based monomer include butadiene, isoprene, chloroprene and the like.

(2) Monomer having acidic polar group The “monomer having an acidic polar group” for synthesizing resin fine particles is not particularly limited, and a conventionally known monomer may be used. Can be. In addition, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics. Specifically, (i) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH), (ii) an α, β-ethylenically unsaturated compound having a sulfone group (—SO ₃ H) (iii ) can be used an unsaturated compound having a phospho group (-PO _2).

(I) Specific examples of the α, β-ethylenically unsaturated compound having a carboxyl group include acrylic acid,
Methacrylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include cinnamic acid, monobutyl maleate, monooctyl maleate, and metal salts thereof (for example, Na salt and Zn salt).

(Ii) Specific examples of the α, β-ethylenically unsaturated compound having a sulfone group include sulfonated styrene, a sodium salt of sulfonated styrene, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and allyl. Na salt of octyl sulfosuccinate and the like can be mentioned.

(Iii) Specific examples of the unsaturated compound having a phospho group (—PO ₂ ) include monomethacryl ethoxy phosphate.

(3) Crosslinkable Monomer Further, a “crosslinkable monomer” may be added in order to improve the properties of the fine resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

In the present invention, the polymerizable monomer includes
Usually, the hydrophobic monomer is used in a range of 85 to 99.9% by weight, and the monomer having an acidic polar group is contained in an amount of 0.1 to 15%.
It is used in the range of weight%.

(Production Method of Resin Fine Particles) The resin fine particles constituting the toner for developing an electrostatic image of the present invention are obtained by emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, interfacial polymerization, or the like. And fine particles obtained by pulverizing a synthetic resin (polymer) obtained by the above polymerization method. Among these, resin fine particles produced by an emulsion polymerization method may be used. preferable. In the present invention, it is preferable to polymerize the resin fine particles in the presence of the fine particles of the release agent from the viewpoint of completely including the fine particles of the release agent in the toner particles.

Examples of the surfactant which can be used in the emulsion polymerization include, for example, sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4- Sodium diazo-bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2
5,5-tetramethyl-triphenylmethane-4,4-
Diazo-bis-β-naphthol-6-sulfonate, etc.), sulfates (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, capric) Sodium, sodium caproate, potassium stearate, calcium oleate, etc.).

The radical polymerization initiator used in the emulsion polymerization can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.), Oxide compounds and the like. Further, the radical polymerization initiator may be used as a redox initiator in combination with a reducing agent, if necessary. By using the redox initiator, the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be further reduced.

Further, the chain transfer agent used for adjusting the initial molecular weight of the obtained polymer (resin fine particles) is not particularly limited, and examples thereof include octyl mercaptan, dodecyl mercaptan and tert-dodecyl mercaptan. Mercaptan is used.

The polymerization temperature for obtaining the resin fine particles is not particularly limited as long as it is not lower than the minimum radical growth temperature of the radical polymerization initiator, and for example, a range of 50 ° C. to 80 ° C. is used. However, it is also possible to polymerize at room temperature or higher by using a combination of a radical polymerization initiator started at room temperature, for example, a hydrogen peroxide-reducing agent (such as ascorbic acid).

<Release Agent Fine Particles> Examples of the release agent fine particles constituting the toner for developing an electrostatic image of the present invention include acid-modified low molecular weight polyethylene (number average molecular weight = 1, 1).
000 to 9,000), acid-modified low molecular weight polypropylene (number average molecular weight = 1,000 to 9000)
0), oxidized wax, and preferably, acid-modified low molecular weight polyethylene, acid-modified low molecular weight polypropylene, oxidized wax and the like. Here, as the oxidized wax, for example, sasol wax (types A1, A2, A3, A14) and the like can be mentioned.
Further, the release agent fine particles are preferably made of a release agent containing a carboxyl group. Here, the release agent fine particles
Low molecular weight polypropylene (number average molecular weight = 1,500-
9,000), low molecular weight polyethylene (number average molecular weight =
1,500-9,000) can also be used in combination. The acid value (B) of the release agent fine particles is preferably 3 or more, and more preferably 5 or more, from the viewpoint of dispersion stability as fine particles in a liquid phase.

The release agent fine particles are used in a state of being dispersed in an aqueous medium (aqueous phase). The dispersion of the release agent particles is
Prepared by adding the release agent particles to an aqueous medium (surfactant aqueous solution) in which the surfactant is dissolved, emulsifying and dispersing under heating, and adding an alkali to adjust the hydrogen ion concentration (pH). can do. Here, the heating temperature at the time of emulsification and dispersion is equal to or higher than the softening point of the release agent fine particles.

<Colorant Fine Particles> Examples of the colorant fine particles to be subjected to heat fusion with the resin fine particles and the release agent fine particles include particles made of inorganic pigments and organic pigments.

As the inorganic pigment constituting the colorant fine particles, any conventionally known inorganic pigment can be used. Specific inorganic pigments are exemplified below. Examples of black inorganic pigments include furnace black, channel black,
Carbon blacks such as acetylene black, thermal black and lamp black, and magnetic powders such as magnetite and ferrite are used. These inorganic pigments can be used alone or in combination of two or more as desired. The amount of the coloring agent fine particles made of an inorganic pigment is 2 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin fine particles.

As the organic pigment constituting the colorant fine particles, any conventionally known organic pigment can be used. Specific organic pigments are exemplified below.

Organic pigments for magenta or red include C.I. 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 Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 5
7: 1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 13
9, C.I. I. Pigment red 144, C.I. I. Pigment Red 149, C.I. I. Pigment Red 166,
C. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222 and the like.

Organic pigments for orange or yellow include C.I. I. Pigment Orange 31, C.I. I. Pigment Orange 43, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15,
C. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I.
I. Pigment Yellow 138 and the like.

Organic pigments for green or cyan include C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15:
3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like. These organic pigments can be used alone or in combination of two or more as desired. The amount of the colorant fine particles made of an organic pigment is 100
2 to 20 parts by weight with respect to parts by weight, preferably 3 to 20 parts by weight.
-15 parts by weight are selected.

It is possible to use a surface modifier for the colorant fine particles, and a conventionally known surface modifier can be used. Specifically, a silane compound,
Titanium compounds and aluminum compounds can be preferably used.

Examples of the silane compound include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane; silizane such as hexamethyldisilozane; γ-chloropropyltrimethoxysilane; vinyltrichlorosilane , Vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane and the like. As a titanium compound, for example, "Plenact" manufactured by Ajinomoto Co.
TTS, 9S, 38 marketed under the trade name
S-1, 41B, 46B, 55, 138S, 238S, etc., commercially available products manufactured by Nippon Soda Co., Ltd. A-1, B-1, TOT, TST,
TAA, TAT, TLA, TOG, TBSTA, A-1
0, TBT, B-2, B-4, B-7, B-10, TB
STA-400, TTS, TOA-30, TSDMA,
TTAB, TTOP and the like. As the aluminum compound, for example, “Plenact AL” manufactured by Ajinomoto Co.
-M "and the like. The concentration of these surface modifiers is 0.01 to 20% by weight, preferably 1 to 15% by weight, based on the colorant fine particles.

The electrostatic image developing toner of the present invention may contain various internal additives and external additives (post-additives).

(Internal Additive) Examples of the internal additive include a charge control agent. Here, a conventionally known charge control agent is used. However, there is a case where an internal additive is not necessary because a monomer having an acidic polar group is copolymerized on the surface of the resin fine particles. Specifically, as a charge control agent having a positive charge property, a nigrosine-based electron donating dye, a metal salt of naphthenic acid or a higher fatty acid, an alkoxylated amine, a quaternary ammonium salt, an alkylamide, a metal complex, a pigment, Examples of the fluorinated activator and the like and the charge control agent having a negative charge property include an electron-accepting organic complex, chlorinated paraffin, chlorinated polyester, and sulfonylamine of copper phthalocyanine.

(External Additives) Examples of the external additives include a fluidizing agent, a charge controlling agent, a lubricant and the like. Examples of such a charge control agent include polyvinylidene fluoride powder, polystyrene powder, polymethyl methacrylate powder, and polyethylene fine particles.

Examples of the fluidizing agent include inorganic fine powders such as silica fine particles, titanium fine particles, alumina fine particles and the like, and sulfides, nitrogen compounds and silicon carbide thereof. Examples of the silica fine particles include commercial products R-805, R-976, and R-97 manufactured by Nippon Aerosil Co., Ltd.
4, R-972, R-812, R-809; HVK-2150, H-200 manufactured by Hoechst Co., Ltd .; commercial products TS-720, TS-530, T manufactured by Cabot Co., Ltd.
S-610, H-5, MS-5 and the like. Examples of the titanium fine particles include commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd .; and commercially available products MT-100S, MT-100B and MT-500B manufactured by Teika Co., Ltd.
S, MT-600, MT-600SS, JA-1; commercially available TA-300SI, TA-5 manufactured by Fuji Titanium Co., Ltd.
00, TAF-130, TAF-510, TAF-51
0T: Commercial products IT-S and IT-O manufactured by Idemitsu Kosan Co., Ltd.
A, IT-OB, IT-OC and the like. Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd .; and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

As the lubricant, for example, cationium, barium, nickel, cobalt, strontium, copper, magnesium, calcium salts of stearic acid; zinc, manganese, iron, cobalt, copper, lead, magnesium salts of oleic acid; palmitic acid Metal salts of higher fatty acids such as zinc, cobalt, copper, magnesium, silicon and calcium salts; zinc, cobalt and calcium salts of linoleic acid; zinc and cadmium salts of ricinoleic acid; lead salts of caprylic acid; and lead salts of caproic acid. No.

[Production Method of Toner for Developing Electrostatic Image] The production method of the present invention comprises resin fine particles [acid value (A)], release agent particles [acid value (B): A <B ≦ A + 20] and coloring. A step of preparing colored particles by aggregating and thermally fusing the agent fine particles. As a method of aggregating and thermally fusing the resin fine particles, the release agent fine particles and the colorant fine particles, a dispersion of the resin fine particles, a dispersion of the release agent fine particles, and a dispersion of the colorant fine particles are mixed. A method in which a coagulant is added to the mixed dispersion and heated is used.

The mixed dispersion of resin fine particles, release agent fine particles and colorant fine particles contains resin fine particles obtained by granulating and polymerizing a monomer in a liquid phase in the presence of the release agent fine particles. It can also be prepared by mixing a dispersion liquid of resin fine particles-release agent fine particles and a dispersion liquid of colorant fine particles.

Preferred forms of the production method of the present invention include:
A method in which a coagulant having a concentration equal to or higher than the critical coagulation concentration of the resin fine particles and an organic solvent which is infinitely soluble in water can be added to the mixed dispersion of the resin fine particles, the release agent fine particles and the colorant fine particles (Japanese Patent Application Laid-Open No. -115572).

According to the above-mentioned production method, the resin fine particles, the release agent fine particles, and the colorant fine particles are aggregated and heat-fused in a liquid phase, and the solid matter is filtered off from the system and dried to obtain colored particles. By adding an external additive to the colored particles, a toner for developing an electrostatic image can be manufactured.

The average particle size (volume average particle size) of the colored particles constituting the toner for developing an electrostatic image of the present invention is usually 3
To 20 μm, and preferably 4 to 15 μm.
Here, the average particle size of the colored particles can be measured using “Coulter Multisizer II” (manufactured by Coulter Inc.). In the toner for developing an electrostatic image of the present invention, the content of the resin component is 97 to 78% by weight, the content of the release agent is 2 to 10% by weight, and the content of the colorant is 1 to 12% by weight. Is preferred.

The electrostatic image developing toner of the present invention may be used as a one-component developer without being mixed with a carrier.
It is preferable to use it as a two-component developer by mixing with a carrier. The toner for developing an electrostatic image of the present invention constituting the one-component developer may be any of a non-magnetic toner containing no magnetic particles and a magnetic toner containing magnetic particles. Here, the particle size of the magnetic particles is about 0.1 to 5 μm.
As the carrier constituting the two-component developer, conventionally known carriers can be used, for example, conventionally known metals such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead. Can be used. Particularly, magnetic particles made of Fe ₂ O ₃ containing at least one of Li ₂ O, MgO and MnO are preferable. The volume average particle diameter of the magnetic particles is 1
The thickness is preferably 5 to 100 μm, and more preferably 20 to 60 μm. The carrier may be formed by coating the surface of the magnetic particles with a known resin such as an olefin resin, a styrene resin, a styrene-acryl resin, a silicone resin, an ester resin, and a fluorine-containing polymer resin. preferable.

[0059]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these embodiments. In the following, “parts” means “parts by weight”.

<Preparation of Colorant Fine Particle Dispersion> 2000 g of carbon black “Mogal L” (manufactured by Cabot)
And 920 g of sodium dodecyl sulfate were added to 13 liters of distilled water, and subjected to a dispersion treatment using an ultrasonic homogenizer and a pressure-type disperser to prepare a dispersion of colorant fine particles. The average particle size of the carbon black in this dispersion was measured using a light scattering electrophoretic particle size analyzer “EL
S-800 "(manufactured by Otsuka Electronics Co., Ltd.)
The average particle size was 82 nm.

<Preparation of Dispersion of Release Agent Fine Particles> [Preparation Example (W-1)] Acid-modified low molecular weight polypropylene (release agent containing a carboxyl group, acid value (B) = 10, number average molecular weight (Mn) ) = 3,300, molecular weight distribution (Mw /
Mn) = 4.5) 250 g of nonylphenoxyethanol (the number of moles of ethoxy unit added: 20, HLB = 1)
The solution was added to 712 g of the aqueous solution of 6), and the pH was adjusted to 9 with potassium hydroxide. The temperature of the system is increased to a temperature equal to or higher than the softening point of the acid-modified low-molecular-weight polypropylene under pressure, and the acid-modified low-molecular-weight polypropylene is emulsified and dispersed to obtain release agent fine particles having a solid content of 26% by weight. (Hereinafter, referred to as “release agent dispersion liquid (W-1)”). The average particle size of the release agent fine particles in the obtained release agent dispersion liquid (W-1) was measured with a light scattering electrophoresis particle size analyzer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.). The particle size was 232 nm.

[Preparation Example (W-2)] Acid-modified low molecular weight polypropylene (release agent containing a carboxyl group, acid value (B) = 20, number average molecular weight (Mn) = 3) as a release agent
300, molecular weight distribution (Mw / Mn) = 4.5) 250 g
Was carried out in the same manner as in Preparation Example (W-1), except that a dispersion of release agent fine particles having a solid content of 26% by weight (hereinafter referred to as “release agent dispersion (W -2) "
That. ) Was prepared. The obtained release agent dispersion (W-
When the average particle size of the release agent fine particles in 2) was measured by a light scattering electrophoresis particle size analyzer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 186 nm.

[Preparation Example (W-3)] Acid-modified low-molecular-weight polypropylene (release agent containing a carboxyl group, acid value (B) = 30, number average molecular weight (Mn) = 3) as a release agent
300, molecular weight distribution (Mw / Mn) = 4.5) 250 g
Was carried out in the same manner as in Preparation Example (W-1), except that a dispersion of release agent fine particles having a solid content of 26% by weight (hereinafter referred to as “release agent dispersion (W -3) "
That. ) Was prepared. The obtained release agent dispersion (W-
The average particle size of the release agent fine particles in 3) was measured by a light scattering electrophoretic particle size analyzer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), and the average particle size was 206 nm.

[Preparation Example (W-4)] Acid-modified low molecular weight polyethylene (a release agent containing a carboxyl group,
Acid value (B) = 15, number average molecular weight (Mn) = 3,50
0, molecular weight distribution (Mw / Mn) = 4.2) Except for using 250 g, emulsification and dispersion treatment was carried out in the same manner as in Preparation Example (W-1) to obtain a release agent having a solid content of 26% by weight. A dispersion liquid of the fine particles (hereinafter, referred to as “release agent dispersion liquid (W-4)”) was prepared. The average particle size of the release agent fine particles in the obtained release agent dispersion liquid (W-4) was measured with a light scattering electrophoresis particle size analyzer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.). The particle size was 184 nm.

<Preparation of Latex (Dispersion of Fine Resin Particles)> [Preparation Example (L-1)] (1) A 2-liter four-headed kolben equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen inlet pipe was prepared by: 986 ml of distilled water, 3.29 g of sodium dodecyl sulfate and 229.
6 g, n-butyl acrylate 80 g, methacrylic acid 10.4 g, tert-dodecyl mercaptan 0.1 g.
212 g, and heated while stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (4.0148 g of potassium persulfate was added to distilled water 2)
Aqueous solution dissolved in 40 ml), and added under a nitrogen stream.
Emulsion polymerization was performed at 70 ° C. for 3 hours. Then, the system was cooled to room temperature to obtain a high molecular weight latex. The average particle size of the resin fine particles in the high molecular weight latex was measured by a light scattering electrophoresis particle size analyzer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).
Met.

(2) Distilled water 24 was placed in a 5-liter four-piece kolben equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introduction pipe.
63 ml, sodium dodecyl sulfate 8.23 g, styrene 632 g, and n-butyl acrylate 144 g
And 24 g of methacrylic acid and 27.39 g of tert-dodecyl mercaptan were charged and heated with stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (potassium persulfate 11.178)
An aqueous solution prepared by dissolving 8 g in 600 ml of distilled water) was added thereto, and emulsion polymerization was carried out at an internal temperature of 70 ° C. for 3 hours under a nitrogen stream. Then, the system was cooled to room temperature to obtain a low molecular weight latex. The average particle size of the resin fine particles in this low molecular weight latex was determined by using a light scattering electrophoresis particle size analyzer “E
As a result of measurement using "LS-800" (manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 81 nm.

(3) The high molecular weight latex obtained in the above (1) and the low molecular weight latex obtained in the above (2) are mixed in a ratio of 20:80 in terms of solid content by weight. , A latex having a solid content of 20% by weight (hereinafter, referred to as
It is referred to as “resin dispersion liquid (L-1)”. ) Was prepared. The glass transition point of the resin fine particles in this resin dispersion (L-1) is 56 ° C., the softening point is 134 ° C., the weight average molecular weight (Mw) is 53,000, the number average molecular weight (Mn) is 8,600, (Mw / Mn) was 6.16.

(4) A part of the resin dispersion (L-1) obtained in the above (3) was taken, and the acid value of the resin fine particles in the resin dispersion (L-1) was measured by an electric conductivity titration method. When (A) was determined, the acid value (A) of the resin fine particles was 5.0.

[Preparation Example (L-2)] (1) 986 ml of distilled water and 3.29 g of sodium dodecyl sulfate were placed in a 2 liter four-headed corven equipped with a cooling tube, a thermometer, a stirrer, and a nitrogen inlet tube. Styrene. 219.
2 g, n-butyl acrylate 80 g, methacrylic acid 20.8 g, tert-dodecyl mercaptan 0.1 g.
212 g, and heated while stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (4.0148 g of potassium persulfate was added to distilled water 2)
Aqueous solution dissolved in 40 ml), and added under a nitrogen stream.
Emulsion polymerization was performed at 70 ° C. for 3 hours. Then, the system was cooled to room temperature to obtain a high molecular weight latex. The average particle size of the resin fine particles in this high molecular weight latex was measured by a light scattering electrophoresis particle size analyzer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.).
Met.

(2) Distilled water was added to a 5-liter four-headed kolben equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introduction pipe.
63 ml, sodium dodecyl sulfate 8.23 g, styrene 608 g, and n-butyl acrylate 144 g
And 60 g of methacrylic acid and 27.39 g of tert-dodecyl mercaptan were charged and heated while stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (potassium persulfate 11.178)
An aqueous solution in which 8 g was dissolved in 600 ml of distilled water) was added, and emulsion polymerization was performed at 70 ° C. for 3 hours under a nitrogen stream. Then, the system was cooled to room temperature to obtain a low molecular weight latex. The average particle size of the resin fine particles in the low molecular weight latex is measured by a light scattering electrophoretic particle size analyzer “ELS”.
-800 "(manufactured by Otsuka Electronics Co., Ltd.), the average particle size was 70 nm.

(3) The high molecular weight latex obtained in the above (1) and the low molecular weight latex obtained in the above (2) are mixed at a ratio of 20:80 in terms of solid content by weight. , A latex having a solid content of 20% by weight (hereinafter, referred to as
It is referred to as “resin dispersion liquid (L-2)”. ) Was prepared. The glass transition point of the resin fine particles in this resin dispersion liquid (L-2) is 57 ° C., the softening point is 135 ° C., the weight average molecular weight (Mw) is 58,000, the number average molecular weight (Mn) is 8,900, (Mw / Mn) was 6.52.

(4) A portion of the resin dispersion (L-2) obtained in the above (3) was taken, and the acid value of the resin fine particles in the resin dispersion (L-2) was measured by an electric conductivity titration method. When (A) was determined, the acid value (A) of the resin fine particles was 10.0
Met.

[Preparation Example (L-3)] (1) 968 ml of distilled water and 3.29 g of sodium dodecyl sulfate were placed in a 2-liter four-headed corven equipped with a cooling tube, a thermometer, a stirrer, and a nitrogen inlet tube. , Release agent dispersion (W
-1) 73.8 g, 229.6 g of styrene, 80 g of n-butyl acrylate, and 10.4 g of methacrylic acid
And 0.212 g of tert-dodecyl mercaptan were charged and heated with stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (an aqueous solution obtained by dissolving 4.0148 g of potassium persulfate in 240 ml of distilled water) was added.
Emulsion polymerization was performed over time. Then, the system was cooled to room temperature to obtain a high molecular weight latex. The average particle size of the resin fine particles in this high molecular weight latex was measured by a light scattering electrophoresis particle size analyzer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.), and the average particle size was 96 nm.

(2) Distilled water was added to a 5-liter 4-headed corven equipped with a cooling pipe, a thermometer, a stirrer, and a nitrogen introduction pipe.
63 ml, sodium dodecyl sulfate 8.23 g, release agent dispersion (W-1) 184.6 g, and styrene 632
g, n-butyl acrylate 144 g, methacrylic acid 24 g, and tert-dodecyl mercaptan 27.3.
9 g, and heated while stirring under a nitrogen stream. When the temperature of the system reached 70 ° C., an aqueous solution of a polymerization initiator (11.788 g of potassium persulfate was added to 60 ml of distilled water)
Aqueous solution dissolved in 0 ml) and added under a nitrogen stream.
Emulsion polymerization was carried out at 0 ° C. for 3 hours. Then, the system was cooled to room temperature to obtain a low molecular weight latex. The average particle size of the resin fine particles in the low molecular weight latex was measured by a light scattering electrophoresis particle size analyzer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), and the average particle size was 93 nm.

(3) The high molecular weight latex obtained in the above (1) and the low molecular weight latex obtained in the above (2) are mixed at a ratio of 20:80 in terms of solid content by weight. , A latex having a solid content of 22% by weight (hereinafter, referred to as
It is referred to as “resin dispersion liquid (L-3)”. ) Was prepared. The glass transition point of the resin fine particles in this resin dispersion liquid (L-3) is 55 ° C., the softening point is 133 ° C., the weight average molecular weight (Mw) is 56,000, the number average molecular weight (Mn) is 8700, and the ratio (Mw). / Mn) was 6.44.

(4) A part of the resin dispersion (L-3) obtained in the above (3) was taken, and the acid value of the resin fine particles in the resin dispersion (L-3) was measured by an electric conductivity titration method. When (A) was determined, the acid value (A) of the resin fine particles was 4.9.

<Example 1> Resin dispersion liquid (L-1) 500
g, 23.08 g of a release agent dispersion (W-1), 80 g of a dispersion of colorant fine particles, and 340 ml of distilled water, and then a 5N aqueous sodium hydroxide solution was added to add p.
H was adjusted to 9.5. The mixed dispersion obtained as described above was charged into a 2-liter four-headed flask equipped with a stirrer, a cooling pipe, and a temperature sensor, and stirred at 156 rpm (tip peripheral speed: 0.65 m / s). While continuing the stirring, an aqueous electrolyte solution (an aqueous solution obtained by dissolving 57.83 g of sodium chloride in 400 ml of distilled water) was added to the mixed dispersion, and isopropyl alcohol 10
4 ml and a surfactant aqueous solution (fluorinated nonionic surfactant “Fluorard FC-170C” (Sumitomo 3M))
Aqueous solution of 20 mg dissolved in 20 ml of distilled water). Next, the temperature of the mixed dispersion was raised to 85 ° C., and stirring was continued for 6 hours, whereby the resin fine particles, the release agent fine particles, and the colorant fine particles were aggregated and thermally fused in a liquid phase. . Next, the solid in the liquid phase was separated by filtration, and distilled water was added to the solid to redisperse the solid.
The pH is adjusted to 13 using an aqueous sodium hydroxide solution of N, and the solid particles are repeatedly filtered and washed with water to remove the surfactant and the electrolyte, and then the solid particles are dried to obtain colored particles. (Hereinafter referred to as “colored particles (1)”).

The volume average particle diameter (d) of the colored particles (1)
₅₀ ) was measured using a “Coulter Multisizer II” (manufactured by Coulter Corporation), and the volume average particle diameter (d ₅₀ ) was measured.
= 6.53 µm, CV = 20%. The amount of the release agent contained in the colored particles (1) determined using a differential scanning calorimeter “DSC-50” (manufactured by Shimadzu Corporation) was 5.8 parts per 100 parts of the resin component.

The toner of the present invention (hereinafter referred to as “toner”) is added to the colored particles (1) by adding hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight. (1) "). The obtained toner (1) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm were
A two-component developer (hereinafter, referred to as "developer (1)") was prepared by mixing the toner at a ratio of 7% by weight.

<Example 2> Resin dispersion liquid (L-2) 500
g, 23.08 g of a release agent dispersion (W-2), 80 g of a colorant fine particle dispersion, and 340 ml of distilled water, and a 5N aqueous sodium hydroxide solution was added thereto.
H was adjusted to 9.5. The mixed dispersion obtained as described above was charged into a 2-liter four-headed flask equipped with a stirrer, a cooling pipe, and a temperature sensor, and stirred at 156 rpm. While continuing the stirring, 96.39 g of an aqueous electrolyte solution (40.39 g of sodium chloride) was added to the mixed dispersion.
Then, 104 ml of isopropyl alcohol and a surfactant aqueous solution (fluorine nonionic surfactant “Fluorard FC-
170C (manufactured by Sumitomo 3M) in 20 ml of distilled water). Next, the temperature of the mixed dispersion was raised to 85 ° C., and stirring was continued for 6 hours, whereby resin fine particles, release agent fine particles,
The coloring agent fine particles were aggregated and thermally fused in the liquid phase. Next, the solid in the liquid phase was separated by filtration, distilled water was added to the solid to redisperse the solid, and the pH was adjusted to 13 with a 5N aqueous sodium hydroxide solution. After repeating the washing with water to remove the surfactant and the electrolyte, the solid matter was dried to obtain colored particles (hereinafter, referred to as “colored particles (2)”).

The volume average particle diameter (d) of the colored particles (2)
₅₀ ) was measured using a “Coulter Multisizer II” (manufactured by Coulter Corporation), and the volume average particle diameter (d ₅₀ ) was measured.
= 6.56 μm, CV = 20%. The amount of the release agent contained in the colored particles (2) was determined using a differential scanning calorimeter “DSC-50” (manufactured by Shimadzu Corporation). The result was 5.5 parts per 100 parts of the resin component.

The colored particles (2) are mixed with hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight, whereby the toner of the present invention (hereinafter referred to as “toner (2) "). The obtained toner (2) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm were
A two-component developer (hereinafter, referred to as “developer (2)”) was prepared by mixing the toner at a ratio of 7% by weight.

Example 3 Colored particles were prepared in the same manner as in Example 2 except that 23.08 g of the release agent dispersion (W-3) was used instead of the release agent dispersion (W-2). (3) was obtained.
When the volume average particle diameter (d ₅₀ ) of the colored particles (3) was measured using “Coulter Multisizer II” (manufactured by Coulter), the volume average particle diameter (d ₅₀ ) was 6.48 μm.
m, CV = 20%. In addition, the differential scanning calorimeter “D
When the release agent contained in the colored particles (3) was quantified using “SC-50” (manufactured by Shimadzu Corporation), resin component 1
It was 5.0 parts per 00 parts. By adding and mixing hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight to the colored particles (3), the toner of the present invention (hereinafter referred to as “toner (3) "). By mixing the obtained toner (3) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm at a ratio where the toner concentration becomes 7% by weight, a two-component developer ( Less than,
It is referred to as “developer (3)”. ) Was prepared.

<Example 4> Colored particles were prepared in the same manner as in Example 1 except that 23.08 g of the release agent dispersion (W-4) was used instead of the release agent dispersion (W-1). (4) was obtained.
When the volume average particle diameter (d ₅₀ ) of the colored particles (4) was measured using “Coulter Multisizer II” (manufactured by Coulter), the volume average particle diameter (d ₅₀ ) was 6.57 μm.
m, CV = 21%. In addition, the differential scanning calorimeter “D
SC-50 "(manufactured by Shimadzu Corporation) was used to quantify the release agent contained in the colored particles (4).
It was 5.8 parts per 00 parts. By adding and mixing hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight to the colored particles (4), the toner of the present invention (hereinafter referred to as “toner (4) "). By mixing the obtained toner (4) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm at a ratio where the toner concentration becomes 7% by weight, a two-component developer ( Less than,
It is referred to as “developer (4)”. ) Was prepared.

Example 5 The procedure of Example 5 was repeated except that 500 g of the resin dispersion (L-3) was used instead of the resin dispersion (L-1), and the release agent dispersion (W-1) was not used. Colored particles (5) were obtained in the same manner as in Example 1. The volume average particle diameter (d ₅₀ ) of the colored particles (5) is referred to as “Coulter Multisizer I”.
Was measured using the I "(manufactured by Beckman Coulter, Inc.), the volume average particle diameter (d ₅₀₎ = 6.72μm, was CV = 21%. The amount of the release agent contained in the colored particles (5) was determined using a differential scanning calorimeter “DSC-50” (manufactured by Shimadzu Corporation). As a result, it was 5.9 parts per 100 parts of the resin component. By adding and mixing hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight to the colored particles (5), the toner of the present invention (hereinafter referred to as “toner (5) "). The obtained toner (5) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm are mixed at a ratio where the toner concentration becomes 7% by weight, whereby a two-component developer ( Hereinafter, “developer (5)” was prepared.

Comparative Example 1 A comparative example was prepared in the same manner as in Example 2 except that 23.08 g of the release agent dispersion (W-1) was used instead of the release agent dispersion (W-2). Colored particles (C
1) was obtained. The volume average particle diameter (d ₅₀ ) of the colored particles (C1) was measured using “Coulter Multisizer II” (manufactured by Coulter, Inc.).
₅₀ ) = 6.60 μm, CV = 20%. The amount of the release agent contained in the colored particles (C1) determined using a differential scanning calorimeter “DSC-50” (manufactured by Shimadzu Corporation) was 5.8 parts per 100 parts of the resin component. By adding and mixing hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight to the colored particles (C1), a comparative toner (hereinafter, referred to as a “toner”) is obtained.
This is referred to as “toner (C1)”. ) Got. By mixing the obtained toner (C1) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm at a ratio where the toner concentration becomes 7% by weight,
Two-component developer (hereinafter referred to as "developer (C1)")
Was prepared.

Comparative Example 2 A comparative example was prepared in the same manner as in Example 1 except that 23.08 g of the release agent dispersion (W-3) was used instead of the release agent dispersion (W-1). Colored particles (C
2) was obtained. The volume average particle diameter (d ₅₀ ) of the colored particles (C2) was measured using “Coulter Multisizer II” (manufactured by Coulter, Inc.).
₅₀ ) = 6.50 μm, CV = 28%. The amount of the release agent contained in the colored particles (C2) determined using a differential scanning calorimeter “DSC-50” (manufactured by Shimadzu Corporation) was 2.4 parts per 100 parts of the resin component. By adding and mixing hydrophobic silica fine particles (primary average particle diameter = 12 nm) as an external additive at a ratio of 2% by weight to the colored particles (C2), a comparative toner (hereinafter, referred to as a “toner”) is obtained.
It is referred to as “toner (C2)”. ) Got. By mixing the obtained toner (C2) and a ferrite carrier coated with a styrene-acrylic resin and having a volume average particle diameter of 30 μm at a ratio where the toner concentration becomes 7% by weight,
Two-component developer (hereinafter referred to as "developer (C2)")
Was prepared.

<Evaluation of Developer> Using each of the developers obtained in Examples 1 to 5 and Comparative Examples 1 and 2, a photosensitive member (laminated organic photosensitive member) and a two-component developer A developing device,
A color electrophotographic copying machine "902" having a heat roller fixing device and being modified so that the set temperature of the heat roller can be variably adjusted.
8 "(manufactured by Konica Corporation), the following items were evaluated. The results are shown in Table 1 below. The heat roller fixing device had a linear pressure of 7 N / cm, a nip width of 3.5 mm, a linear velocity of 210 mm / sec, and did not have a cleaning mechanism.

(1) Measurement of fixable temperature range: The fixable temperature range was measured by changing the set temperature of the heat roller stepwise (in steps of 10 °) within a range of 100 to 250 ° C. Here, the occurrence of the offset phenomenon was confirmed by forming a fixed toner image using a document having a solid black portion with a width of 10 mm at the leading end of the image, and immediately thereafter, heating the blank transfer paper under the same conditions. It was sent to a roller fixing device to visually observe whether or not toner contamination occurred.

(2) Image Smearing: A continuous copy of 50,000 times was performed using a document having a pixel ratio of 5% by a modified color electrophotographic copying machine “9028” (manufactured by Konica Corporation) under the following conditions. After a lapse of 24 hours, a blank document was copied and the stained state in the copied image was visually observed.

[Conditions] Surface potential of photoreceptor (laminated organic photoreceptor): -550 V DC bias: -250 V AC bias: Vp-p: -50 to -450 V Alternating electric field frequency: 1800 Hz Minimum gap (Dsd): 300 μm ・ Pressing regulating force: 10 gf / mm ・ Pressing regulating rod: SUS416 (made of magnetic stainless steel)
/ Diameter 3mm ・ Developer layer thickness: 150μm ・ Developing sleeve: 20mm ・ Set temperature of heat roller: 180 ℃ ・ Environmental conditions: temperature 25 ℃, relative humidity 30%

[0092]

[Table 1]

Toners (1) obtained in Examples 1 to 5
(5) had good releasability and a wide fixing temperature range. On the other hand, the toner (C1) obtained in Comparative Example 1
Since the acid value (B) of the release agent fine particles was equal to the acid value (A) of the resin fine particles, the releasability was low and the fixable temperature range was narrow. Further, in the toner (C2) obtained in Comparative Example 2, the difference between the acid value (B) of the release agent fine particles and the acid value (A) of the resin fine particles exceeds 20, and therefore,
The releasability was extremely low, and the fixing temperature range was narrow.

[0094]

The toner for developing electrostatic images of the present invention has good releasability and has a wide fixable temperature range. ADVANTAGE OF THE INVENTION The manufacturing method of this invention has favorable releasability and can manufacture the toner for electrostatic image development with a wide fixable temperature range.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Mikio Kamiyama 1 Sakuracho, Hino-shi, Tokyo Konica Corporation F-term (reference) 2H005 AA01 AA06 AA08 AB03 AB06 CA04 CA13 CA14 CA18 CB18 EA06 EA10

Claims (8)

[Claims] 1. An electrostatic image developing toner comprising colored particles obtained by aggregating and thermally fusing resin fine particles, release agent fine particles and colorant fine particles, wherein the resin fine particles have an acid value of A, When the acid value of the release agent particles is B, the toner for developing an electrostatic charge image satisfies the condition represented by the following formula 1. (Equation 1) 0 <BA ≦ 20 2. The electrostatic image development according to claim 1, wherein the resin fine particles are made of a thermoplastic copolymer containing at least one kind of acidic polar group selected from a carboxyl group, a sulfone group and a phospho group. For toner. 3. The electrostatic image developing toner according to claim 1, wherein the release agent fine particles comprise a release agent containing a carboxyl group. 4. The release agent particles according to claim 1, wherein the fine particles of the release agent comprise at least one release agent selected from acid-modified low-molecular-weight polypropylene, acid-modified low-molecular-weight polyethylene and oxidized wax. For developing electrostatic images. 5. A dispersion in which release agent fine particles comprising at least one release agent selected from acid-modified low molecular weight polypropylene, acid-modified low molecular weight polyethylene and oxidized wax are dispersed in an aqueous phase, and a dispersion of resin fine particles. And a colorant obtained by coagulating and thermally fusing the resin fine particles, the release agent fine particles, and the colorant fine particles by mixing with a dispersion of colorant particles. Item 6. An electrostatic image developing toner according to Item 4. 6. A resin fine particle formed by subjecting a monomer to granulation polymerization in a liquid phase in the presence of a release agent fine particle, and the release agent fine particle and the colorant fine particle are aggregated and thermally fused. When the acid value of the resin fine particles is A and the acid value of the release agent fine particles is B, the condition represented by the following formula 1 is satisfied. Item 6. The electrostatic image developing toner according to any one of Items 4. (Equation 1) 0 <BA ≦ 20 7. A method for producing a toner for developing an electrostatic charge image, comprising a step of aggregating and thermally fusing resin fine particles, release agent fine particles and colorant fine particles to prepare a colored particle. A, wherein the acid value of the releasing agent fine particles is B, and the condition represented by the following formula 1 is satisfied: (Equation 1) 0 <BA ≦ 20 8. A resin fine particle formed by subjecting a monomer to granulation polymerization in a liquid phase in the presence of a release agent fine particle, and the release agent fine particle and the colorant fine particle are aggregated and thermally fused. A process for preparing colored particles, wherein when the acid value of the resin fine particles is A and the acid value of the release agent fine particles is B, the electrostatic charge image satisfies the condition shown in the following formula 1. A method for producing a developing toner. (Equation 1) 0 <BA ≦ 20