JP2001235895A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-cost electrostatic charge image developing toner excellent in oilless fixability. SOLUTION: The surface of a toner having 2-20 μm average particle diameter is coated with fine resin particles having 0.1-1 μm average particle diameter and including 2-50 parts wax and the particles are fixed or fused to obtain the objective electrostatic charge image developing toner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used in an electrophotographic copying machine and a printer. More specifically, the present invention relates to a toner for developing an electrostatic charge image having an oil-less fixing property.

[0002]

2. Description of the Related Art In recent years, electrophotographic copying machines and printers have
In order to reduce the cost, there is a tendency to downsize the apparatus. As one of the measures, an oil-less fixing electrostatic image developing toner which does not require a silicon oil tank or a coating apparatus is desired. In response to such demands, attempts have been made to increase the degree of polymerization of the toner binder resin to increase the viscoelasticity, or to include a large amount of wax in the toner (Japanese Patent Laid-Open No. 50368/1996).
In the former, the energy cost required for fixing is large, and in the latter, the kneading and pulverization method is not sufficient for the wax content, so the emulsion is produced by emulsion polymerization or suspension polymerization, but in order to contain a large amount of wax. However, there was a disadvantage that the cost of the wax was large.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of the conventionally used toner for developing an electrostatic image for oil-less fixing, has low cost, and has low-temperature fixability. An object of the present invention is to provide a toner for developing an electrostatic image to which a new oil-less fixing property is imparted.

[0004]

Means for Solving the Problems The above-mentioned problems have an average particle diameter of 2 to 2.
The average particle size is 0.1 μm on the surface of the core toner having a particle size of 20 μm.
By coating and fixing or fusing resin fine particles having a wax content of 2 to 50 parts and having a thickness of 1 to 1 [mu] m, oil-less fixability is imparted and solved. A feature of the present invention resides in that wax is included in the fine particles covering the surface.

[Detailed Description of the Invention] Hereinafter, the present invention will be described in detail.
The core toner used in the present invention may be used for low-temperature fixing property, for general fixing temperature, or for high-temperature fixing property. The core toner and the resin fine particles may be selected together. Particularly, Tg of the core toner is 30 to 110 ° C.
A resin made of the above binder resin can be suitably used.
If the Tg is lower than 30 ° C., it may be difficult to produce the core toner and it may be difficult to balance with the storage stability.
On the other hand, when Tg is higher than 110 ° C., the energy cost increases, and the significance of imparting the oilless fixing property may be reduced, which is not preferable.

[0006] The composition of the core toner used in the present invention may be any of the compositions of commonly used toners, such as those obtained by kneading a binder resin and a colorant, a charge controlling agent, a wax, etc., and pulverizing or freeze-pulverizing. Or a mixture obtained by suspension polymerization of a mixture of a binder resin component monomer and a colorant, a charge control agent, wax, or a latex obtained by emulsion polymerization of a binder resin component monomer and a colorant, a charge control agent, wax, etc. A mixture of a wax-encapsulated latex and a colorant, a charge controlling agent, etc., which is obtained by coagulating and growing a mixture of particles having an arbitrary particle size, and a wax emulsion is used as a seed, and a mixture of a wax-encapsulated latex obtained by emulsion polymerization of a monomer is coagulated and grown to an arbitrary particle size. Molded ones can be used. The volume average particle size of the core toner is usually 2 to 20 μm, preferably 3 to 11 μm.

As the base resin which is a main component of the core toner, any resin which is usually used as a binder resin for a toner can be used. For example, polystyrene resin, polyester resin, polyacrylate resin, styrene resin
Acrylic acid ester copolymer resin, styrene-methacrylic acid ester copolymer resin, ternary or multi-component resin of styrene and acrylic acid ester or methacrylic acid ester and acrylic acid or methacrylic acid, polyvinyl chloride resin, polyacetic acid Vinyl resin, epoxy resin and the like can be used. As the colorant, a colorant generally used for a black toner and a full color toner can be used, and any of an inorganic pigment, an organic pigment, an organic dye, or a combination thereof may be used. Specific examples of these include carbon black, nigrosine dye,
Aniline blue, chrome yellow, phthalocyanine blue, oil red, phthalocyanine green, hansa yellow, rhodamine dye, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, condensed azo dye, etc. These known dyes and pigments can be used alone or in combination.

In the case of a full-color toner, it is preferable to use benzidine yellow for yellow, monoazo and condensed azo dyes and pigments, magenta for quinacridone and monoazo dyes and cyan for phthalocyanine blue. The amount of the colorant used is usually the base resin 1 of the core toner.
It is used in an amount of 1 to 20 parts by weight with respect to 00 parts by weight. Further, a charge controlling agent, a wax and the like can be optionally used. As the charge control agent, any known compounds can be used alone or in combination. Examples thereof include a quaternary ammonium salt as a positive charge, a basic / electron donating metal substance, and a negative charge. Examples include metal chelates, metal salts of organic acids, metal-containing dyes, nigrosine dyes, amide group-containing compounds, phenol compounds, naphthol compounds and their metal salts, urethane bond-containing compounds, and acidic or electron-withdrawing organic substances.

In consideration of the color toner adaptability (the charge control agent itself is colorless or light color and there is no hindrance to the toner), a quaternary ammonium salt compound is used as the positive charge, and salicylic acid is used as the negative charge. Or metal salts and metal complexes of alkyl salicylic acid with chromium, zinc, aluminum, etc., metal salts and metal complexes of benzylic acid,
Amide compounds, phenol compounds, naphthol compounds,
Phenolamide compound, 4,4'-methylenebis [2
Hydroxynaphthalene compounds such as-[N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] are preferred. The amount to be used may be determined depending on the desired charge amount of the toner, but is usually 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the base resin of the core toner.

As the wax used for the core toner, any known waxes can be used, and paraffinic, olefinic, natural and synthetic fatty acid esters, fatty acid amides, and long-chain alkylketone resin resins can be used. And one or a mixture of denatured silicone resin-based, specifically, olefin-based wax such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, copolymerized polyethylene, etc., having natural and synthetic long-chain aliphatic groups. Examples thereof include an ester wax, a ketone having a long-chain alkyl group, silicon having an alkyl group or a phenyl group, a higher fatty acid or a higher fatty acid amide. The used amount is 0 to 20 parts by weight, preferably 0 to 10 parts by weight, and more preferably 2 to 20 parts by weight based on 100 parts by weight of the base resin of the core toner.
It is preferred to use 10 parts by weight. If the amount of the wax is too large, it causes a cost increase and the advantage of the present invention is impaired.

The Tg of the resin used as the base of the resin fine particles used in the present invention is desirably 50 to 110 ° C.
When the Tg is lower than 50 ° C., the storage stability of the toner becomes unstable, and when the Tg is higher than 110 ° C., it is not realistic.
Further, the energy cost is undesirably increased.
The type of resin used as the base of the resin fine particles is, for example, one of diallyl phthalate resin (PDAP) or diallyl isophthalate resin (PDAIP) and copolymer resin of diallyl phthalate and diallyl isophthalate (COPDAP).
Species or mixtures, and copolymer resins of these with acrylic esters, polystyrene resins, polyester resins, polyacrylate resins, styrene-acrylate copolymer resins, styrene-methacrylate copolymer resins, polychlorinated Vinyl resin, polyvinyl acetate resin,
Epoxy resin, styrene-acrylic acid copolymer resin, styrene-methacrylic acid copolymer resin, styrene-acrylic acid ester-acrylic acid terpolymer resin, styrene-acrylic acid ester-methacrylic acid terpolymer resin , Methacrylic acid ester-acrylic acid ester-acrylic acid terpolymer resin, methacrylic acid ester-acrylic acid ester-methacrylic acid terpolymer resin and the like can be used, preferably, styrene and acrylic acid ester or methacrylic acid. Copolymer resins with esters or terpolymer resins of styrene with acrylic esters or methacrylic esters and acrylic acid or methacrylic acid are preferred.

The preferred particle size of the resin fine particles varies depending on the particle size of the core toner, but is preferably 0.1 to 1 μm for a toner having an average particle size of 3 to 11 μm. The amount of the oil-less fixing property imparting resin fine particles depends on the balance between the particle diameter of the core toner and the particle diameter of the resin fine particles, and is preferably about 1 to 50% by weight, and Is preferred, and 5 to 20% by weight is particularly preferred. When the amount of the resin fine particles for imparting the oilless fixing property is less than 1% by weight, the oilless fixing property cannot be sufficiently exhibited, and when the amount is more than 50% by weight, the effect of imparting the oilless fixing property is sufficiently exhibited. And the cost reduction effect is undesirably reduced.

As the wax used for the resin fine particles used in the present invention, the same wax as the wax used for the core toner can be used. For example, paraffin type, olefin type, natural and synthetic fatty acid ester type can be used. One or a mixture of fatty acid amide type, long chain alkyl ketone resin type and modified silicone resin type, and specifically, olefinic waxes such as low molecular weight polyethylene, low molecular weight polypropylene, copolymerized polyethylene, Ester waxes having natural and synthetic long-chain aliphatic groups, ketones having long-chain alkyl groups, silicon having alkyl groups or phenyl groups, higher fatty acids or higher fatty acid amides,
And the like. Of these, fatty acid ester waxes are preferred. Specific examples of the fatty acid ester wax include alkanoic acid esters such as stearyl stearate and behenyl behenate; and alkanoic acid esters of polyhydric alcohols such as stearic acid ester of pentaerythritol. The amount of wax contained in the resin fine particles is 2 parts per 100 parts by weight of the base resin.
It is preferable to use 50 to 50 parts by weight, preferably 3 to 25 parts by weight. When the amount of the wax is less than 2 parts by weight, the oilless fixing property cannot be sufficiently exhibited, and when the amount is more than 50 parts by weight, the effect of imparting the oilless fixing property is sufficiently exhibited, but the toner strength is reduced and the storage stability is deteriorated. It is not preferable because the cost reduction effect is weakened due to instability and a large amount of wax used, and it is difficult to manufacture wax-encapsulated resin fine particles. In order to effectively exhibit low-temperature fixability, the wax content of the resin fine particles is preferably larger than the wax content of the core toner.

The method for producing the wax-encapsulated resin fine particles is not particularly limited, but is preferably obtained by seed polymerization of the monomer mixture using the wax fine particles as a seed.

Although the reason why the toner of the present invention exhibits excellent oil-less fixability is not necessarily clear, since the wax is present near the surface of the toner, the wax is efficiently removed from the toner particles at the initial stage of fixing. Presumed to be due to leaching. Therefore, by employing the present invention, the total amount of wax required to exhibit the same oil-less fixability is reduced as compared with the case where the wax is present at the center of the toner particles or the case where the wax is dispersed throughout the toner particles. can do. In particular, when the core toner is manufactured by the kneading and pulverizing method, the amount of wax that can be contained in the toner is usually limited to about 10% or less. An embodiment in which resin fine particles containing the above are fixed or fused is effective.

[0016]

The present invention will be specifically described below with reference to examples. In the following examples, “parts” means “parts by weight”. In addition, the average particle size, average molecular weight, glass transition point (T
g) and the fixing temperature range were measured by the following methods. Average particle size : Measured using LA-500 manufactured by Horiba, Microtrac UPA manufactured by Nikkiso Co., Ltd., and Coulter Counter Multisizer II (produced by Coulter Counter). Average molecular weight : measured by gel permeation chromatography (GPC) (apparatus: GPC manufactured by TOSO)
Apparatus HLC-8020, column: Polymer La
PL-gel Mixed-B manufactured by boratory
10 μ, solvent: THF, sample concentration: 0.1 wt%, calibration curve: standard polystyrene) glass transition point (Tg) : DSC7 manufactured by PerkinElmer
(The temperature was raised from 30 ° C to 100 ° C in 7 minutes, rapidly cooled from 100 ° C to -20 ° C, and
The temperature was raised to 00 ° C. in 12 minutes, and the Tg value observed during the second temperature increase was used). Fixing temperature range : When a recording paper carrying an unfixed toner image is prepared, the surface temperature of the heating roller is changed from 100 ° C. to 220 ° C. (or 200 ° C.), and is conveyed to the fixing nip portion and discharged. Was observed. A temperature region in which toner offset did not occur on the heating roller during fixing and the toner on the recording paper after fixing was sufficiently adhered to the recording paper was defined as a fixing temperature region. The heating roller of the fixing device is made of aluminum as a core metal and 1.5 m of a dimethyl low-temperature vulcanized silicone rubber having a rubber hardness of 3 ° according to JIS-A standard as an elastic layer.
m, PFA (tetrafluoroethylene-
Perfluoroalkyl vinyl ether copolymer) 50μ
The thickness of the fixing roller is 80 mm, the diameter is 30 mm, and the rubber hardness of the fixing roller surface is 80 as measured in accordance with Japan Rubber Association Standard SRIS 0101. Without applying silicone oil, the nip width was evaluated at 4 mm. Fixing speed is 12
The test was performed at 0 mm / s. Evaluation range is 100 to 220 ° C
Therefore, for those having an upper limit of the fixing temperature of 220 ° C., the true upper limit of the fixing temperature may be even higher.

(1) Production of core toner (1-A) Kneading and pulverization method toner Styrene / acrylic resin 100 parts (Mw 34,000, Tg 30 ° C.) Cyan pigment 6 parts Paraffin wax 5 parts Charge control agent P-51 2 parts Was kneaded with a twin screw extruder kneader PCM30 (manufactured by Ikegai Iron Works), and crushed and classified to obtain a toner (A) having an average particle size of 8.4 μm in a Coulter counter.

(1-B) Kneading and pulverizing method toner Styrene / acrylic resin 100 parts (Mw 34,000, Tg 50 ° C.) Cyan pigment 6 parts Paraffin wax 5 parts Charge control agent P-51 2 parts The mixture was kneaded with PCM30 (manufactured by Ikegai Iron Works), crushed and classified to obtain a toner (B) having an average particle size of 9.1 μm in a Coulter counter.

(1-C) Kneading and pulverizing toner 100 parts styrene / acrylic resin (Mw 90,000, Tg 60 ° C.) Cyan pigment 6 parts Paraffin wax 5 parts Charge control agent P-51 2 parts Biaxial extruder PCM30 ( (Ikegai Iron Works), pulverized and classified to obtain a toner (C) having an average particle size of 7.9 μm in a Coulter counter.

(1-D-1) Emulsion Polymerization Aggregated Toner Slurry (Polymer Primary Particle Dispersion) Equipped with a stirrer (three retreating blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries. 5.3 parts of a 10% aqueous solution of sodium dodecylbenzenesulfonate was placed in a reactor (volume 21, inner diameter 120 mm),
Deionized water (311 parts) was charged, the temperature was raised to 90 ° C. under a nitrogen stream, and 6.4 parts of a 2% aqueous hydrogen peroxide solution and 6.4 parts of a 2% aqueous ascorbic acid solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of polymerization, and the aqueous initiator solution was added over 6 hours from the start of polymerization,
Hold for another 30 minutes.

[Monomers] Styrene 59 parts Butyl acrylate 39 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 part 1% 2-mercaptoethanol aqueous solution 3 parts [Emulsifier aqueous solution] 10% aqueous sodium dodecylbenzenesulfonate 2.7 Part 1% polyoxyethylene nonylphenyl ether aqueous solution 1.1 part Demineralized water 22 parts [Initiator aqueous solution] 2% hydrogen peroxide aqueous solution 36 parts 2% ascorbic acid aqueous solution 36 parts After completion of the polymerization reaction, the mixture is cooled to give a milky white polymer dispersion. A liquid was obtained.
The weight average molecular weight of the THF soluble portion of the polymer is 54.00.
0, the average particle diameter measured by UPA was 154 nm, and Tg was 40 ° C.

(Colorant Fine Particle Dispersion) Pigment Blue 1
The average particle size measured by UPA with a 5: 3 aqueous dispersion (EP-700 Blue GA, manufactured by Dainichi Seika, solid content: 35%) was 150 nm. (Charge control agent fine particle dispersion) 4,4'-methylenebis [2
20 parts of-[N- (4-chlorophenyl) amide] -3-hydroxynaphthalene, 4 parts of alkylnaphthalenesulfonate and 76 parts of demineralized water were dispersed in a sand grinder mill to obtain a charge control agent fine particle dispersion. . The average particle size measured by UPA was 200 nm. (Production of core toner) Polymer primary particle dispersion 100 parts (as solid content) Paraffin wax (LUVAX-1266, manufactured by Nippon Seiwa) 5 parts (as solid content) Colorant fine particle dispersion 6 parts (as solid content) Toner) 0.6 part (as solid content) of charge control agent fine particle dispersion A toner was produced by the following procedure using each of the above components. A polymer primary particle dispersion, a paraffin wax dispersion, a colorant fine particle dispersion, and a charge control agent dispersion were charged into a reactor (volume: 1 liter, Disper) and uniformly mixed. The pH of the resulting mixed dispersion was adjusted to 3.5 while stirring. Thereafter, the temperature was increased while stirring to obtain a particle size of 5.5.
When the pH reached μm, the pH was adjusted to 7 and
To 1 hour, and then cooled to obtain an aggregated toner slurry (solid content concentration: 22.3%) (D-1).

(1-D-2) Emulsion Polymerization Aggregated Toner A part of the aggregated toner slurry obtained in (D-1) is filtered and
After washing and drying, an aggregated toner (D-2) was obtained.

(1-E) Suspension polymerization toner 60 parts styrene 39.6 parts butyl acrylate 0.4 parts divinylbenzene 4 parts carbon black (MA100S manufactured by Mitsubishi Chemical) 4 parts paraffin wax (LUVAX-1266 manufactured by Nippon Seiro) 5 parts A monomer mixture was prepared by mixing and dispersing 1.5 parts of a dispersant (Dispalon, manufactured by Kusumoto Kasei) and 5 parts of a polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) by a conventional method. Separately, a mixed dispersion of 25 parts of tricalcium phosphate, 0.05 parts of sodium polyacrylate, 200 parts of calcium chloride, and 300 parts of demineralized water is prepared, and a monomer mixture is added thereto to prepare a suspension. Polymerization by suspension method, acid washing, filtration, washing with water and drying, followed by Mw 33,000, resin T
g 40 ° C., average particle size 6.9 in coulter counter
As a result, a μm suspension polymerization toner (E) was obtained.

(1-F) Suspension Polymerized Toner The monomer mixture composition is as follows: styrene 67 parts butyl acrylate 32.6 parts divinylbenzene 0.4 parts carbon black MA100S 4 parts paraffin wax (LUUVAX-1266) 5 parts dispersant (disparone) ) 1.5 parts polymerization initiator (V-65) Except for using 5 parts, suspension polymerization was carried out in the same manner as in (1-E), and Mw 3.
A suspension-polymerized toner (F) having a particle size of 20,000, a resin Tg of 50 ° C. and an average particle size of 8.2 μm as measured by a Coulter counter was obtained.

(2) Production of Wax-Encapsulated Resin Fine Particles (2-G) Paraffin-Wax-Encapsulated Resin Fine Particles A mixture of styrene / butyl acrylate / acrylic acid = 75.2 / 22.8 / 2 monomer 90 parts with paraffin wax ( LUVAX-1266 Nippon Seisaku) 10 parts were dissolved uniformly, emulsified with sodium dodecylbenzenesulfonate, emulsion-polymerized with hydrogen peroxide as initiator, Mw 74,000, resin Tg 65 ° C, measured with UPA A paraffin wax-encapsulated resin fine particle latex (G) having an average particle diameter of 0.206 μm and a resin concentration of 20 wt% was obtained.

(2-H) Ester wax-encapsulated resin fine particles (wax dispersion) 69.74 parts of demineralized water, an ester mixture mainly composed of behenyl behenate (Unistar M-22)
30 parts of 22SL (manufactured by NOF Corporation), 0.23 part of sodium dodecylbenzenesulfonate, and 0.03 part of polyoxyethylene nonylphenyl ether were mixed and emulsified by high-pressure shear to obtain a dispersion of fine particles of ester wax. L
The average particle size of the ester wax fine particles measured by A-500 was 820 nm. (Resin Fine Particle Dispersion) 35 parts of the above wax dispersion was placed in a reactor (volume 21, inner diameter 120 mm) equipped with a stirrer (three retreating blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. 328 parts of demineralized water were charged and the temperature was raised to 90 ° C. under a nitrogen stream, and 6.4 parts of a 2% aqueous hydrogen peroxide solution,
6.4 parts of a 10% aqueous ascorbic acid solution were added. afterwards,
The following mixture of the monomer and the aqueous solution of the emulsifier was added over 5 hours from the start of the polymerization, and the aqueous solution of the initiator was added over 6 hours from the start of the polymerization.

[Monomers] Styrene 75.2 parts Butyl acrylate 22.8 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 parts 1% 2-mercaptoethanol aqueous solution 3 parts [Emulsifier aqueous solution] 10% sodium dodecylbenzenesulfonate Aqueous solution 2.7 parts 1% polyoxyethylene nonyl phenyl ether aqueous solution 1.1 parts Demineralized water 22 parts [Initiator aqueous solution] 2% hydrogen peroxide aqueous solution 36 parts 2% ascorbic acid aqueous solution 36 parts (H) was obtained. The weight average molecular weight of the THF soluble portion of the polymer is 71.
000, average particle size measured by UPA is 254 nm, T
g was 65 ° C.

(2-I) Ester Wax-Encapsulated Resin Fine Particles In the same manner as (2-H) except that the number of monomers was 72 parts for styrene, 21 parts for butyl acrylate and 2 parts for acrylic acid, Mw was 69,000 and T was
g 60 ° C., average particle diameter 0.244 μ measured by UPA
m, an ester wax-encapsulated resin fine particle latex (I) having a resin concentration of 20 wt% was obtained.

(2-J) Ester Wax-Encapsulated Resin Fine Particles In the same manner as in (2-H) except that the number of monomers is 72 parts for styrene, 26 parts for butyl acrylate, and 2 parts for acrylic acid, the resin has a Mw of 54,000 and a resin of Tg 60 ° C., average particle size 0.206 measured by UPA
An ester wax-encapsulated resin fine particle latex (J) having a resin concentration of 20 wt% was obtained. (2-K) Ester-based wax-encapsulated resin fine particles (2-K) except that the wax dispersion was changed to the following.
In the same manner as in H), an ester wax-encapsulated resin fine particle latex (K) having an Mw of 140,000, an average particle diameter of 201 nm measured by UPA, and a resin concentration of 20 wt% was obtained. (Wax dispersion) 68 parts of demineralized water, 30 parts of stearic acid ester of pentaerythritol (Unistar H476 manufactured by NOF Corporation) and 0.25 part of sodium dodecylbenzenesulfonate were mixed, emulsified by applying high pressure shearing at 90 ° C., and esterified. A dispersion of wax microparticles was obtained. LA-5
The average particle size of the ester wax fine particles measured at 00 was 3
It was 50 nm.

<Example 1> 50 parts of wax-encapsulated resin microparticle latex (G) 50 parts of demineralized water 600 parts were placed in a reaction vessel, and 100 parts of toner (A) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 35 ° C., and the reaction was continued for 2 hours. After the resin fine particles were fixed to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 110 to 145 ° C.

Example 2 50 parts of wax-encapsulated resin fine particle latex (H), 600 parts of demineralized water were placed in a reaction vessel, and 100 parts of toner (B) was gradually stirred at room temperature at 300 revolutions with a flat blade stirrer. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 50 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 135 to 165 ° C.

<Example 3> 50 parts of wax-encapsulated resin fine particle latex (I) 50 parts of demineralized water 600 parts were placed in a reaction vessel, and 100 parts of toner (B) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 50 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 130 to 165 ° C.

Example 4 50 parts of wax-encapsulated resin fine particle latex (J) 50 parts of deionized water 600 parts were placed in a reaction vessel, and 100 parts of toner (B) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 50 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 125 to 175 ° C.

Example 5 Wax-encapsulated resin fine particle latex (I) 50 parts Deionized water 600 parts was placed in a reaction vessel, and 100 parts of toner (C) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 60 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 135 to 175 ° C.

Example 6 50 parts of wax-encapsulated resin microparticle latex (I) 50 parts of deionized water 600 parts were placed in a reaction vessel, and 100 parts of toner (D-2) was stirred at room temperature with a flat blade stirrer at 300 rotations. Was gradually added and uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 60 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 110 to 165 ° C.

Example 7 50 parts of wax-encapsulated resin fine particle latex (I) 50 parts of deionized water 600 parts were placed in a reaction vessel, and 100 parts of toner (E) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 60 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 115 to 160 ° C.

<Example 8> 50 parts of wax-encapsulated resin fine particle latex (I), 600 parts of demineralized water were placed in a reaction vessel, and 100 parts of toner (F) was gradually stirred at room temperature with a flat blade stirrer at 300 rotations. And uniformly dispersed. Next, the pH was adjusted to 3.0 with stirring, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was raised to 60 ° C., and the reaction was continued for 2 hours. After fixing the resin fine particles to the core toner, filtration, washing and drying were performed to obtain a resin fine particle fixed toner. When the fixing property of this resin fine particle fixed toner was evaluated,
It was confirmed that fixing was performed in a temperature range of 125 to 165 ° C.

Example 9 450 parts of agglomerated toner slurry (D-1) (solids concentration: 22.3%) 50 parts of wax-encapsulated resin fine particle latex (I) were placed in a reaction vessel, and were stirred at room temperature with a flat blade stirrer. The pH was adjusted to 3.0 while stirring at 300 rotations, and the reaction was allowed to proceed until the dispersion liquid did not become cloudy. Subsequently, the reaction temperature was set to 50 ° C.
Then, the reaction was continued for 2 hours to fix the resin fine particles on the core toner, followed by filtration, washing and drying to obtain a resin fine particle fixed toner. When the fixing property of the resin fine particle-fixed toner was evaluated, it was confirmed that the toner was fixed in a temperature range of 110 to 165 ° C.

<Comparative Example 1> The toner (A) was evaluated for fixing properties in the same manner as in Example 1.
It was confirmed that any offset was found in the temperature range of ° C. (200 ° C. or higher was not performed).

<Comparative Example 2> The toner (B) was evaluated for fixing properties in the same manner as in Example 2.
It was confirmed that any offset was found in the temperature range of ° C. (200 ° C. or higher was not performed).

<Comparative Example 3> The toner (C) was evaluated for fixability in the same manner as in Example 5.
It was confirmed that any offset was found in the temperature range of ° C. (200 ° C. or higher was not performed).

<Comparative Example 4> The toner (D-2) was evaluated for fixing properties in the same manner as in Example 6.
It was confirmed that the image was fixed in a narrow temperature range of 25 ° C., but it was confirmed that the temperature was offset in any temperature range up to 200 ° C. (200 ° C. or more was not performed). .

<Comparative Example 5> The toner (E) was evaluated for fixability in the same manner as in Example 7.
It was confirmed that the toner was fixed in a narrow temperature range of ℃.
It was confirmed that the temperature was offset in any temperature range up to 200 ° C. (200 ° C. or higher was not performed).

<Comparative Example 6> The toner (F) was evaluated for fixability in the same manner as in Example 8.
It was confirmed that the toner was fixed in a narrow temperature range of ℃.
It was confirmed that the temperature was offset in any temperature range up to 200 ° C. (200 ° C. or higher was not performed). <Example 10> Instead of wax-containing latex (G) in Example 1, wax-containing latex (K)
Except for using the above, a resin fine particle fixed toner was obtained in the same manner as in Example 1. When the fixing property of the resin fine particle fixed toner was evaluated, it was confirmed that the toner was fixed in a temperature range of 110 to 150 ° C. <Example 11> In Example 6, wax-containing latex (K) was used instead of wax-containing latex (I).
Except for using, a toner with resin fine particles fixed was obtained in the same manner as in Example 6. When the fixing property of the resin fine particle fixed toner was evaluated, it was confirmed that the toner was fixed in a temperature range of 110 to 175 ° C. Table 1 summarizes the above results.

[0046]

[Table 1]

[0047]

According to the method of the present invention, a toner having an oil-less fixing property can be easily produced.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tomoko Ishikawa 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Yokohama Research Laboratory F-term (reference) 2H005 AA08 AB04 AB09 CA04 CA14 DA06 EA03 EA05 EA07

Claims (5)

[Claims] 1. A base resin having an average particle size of 0.1 to 1 μm on a surface of a core toner having an average particle size of 2 to 20 μm.
A toner for developing an electrostatic image, which is coated with resin fine particles containing 2 to 50 parts by weight of wax with respect to 00 parts by weight and fixed or fused. 2. The base resin of the resin fine particles comprises a ternary or multi-component copolymer resin of styrene and an acrylate or methacrylate and an acrylic or methacrylic acid, and has a glass transition point (Tg) of 50 to 11.
2. The toner for developing an electrostatic image according to claim 1, wherein the temperature is 0.degree. 3. The wax is one of fatty acid ester compounds.
Or a mixture of two or more thereof, and the compound has a melting point of 50
The toner for developing an electrostatic charge image according to claim 1, wherein the temperature is from −95 ° C. 4. The electrostatic image developing toner according to claim 1, wherein the core toner is produced by a kneading and pulverizing method. 5. The core toner contains 2 to 10 parts by weight of a wax with respect to 100 parts by weight of a base resin.
The resin fine particles contain 3 to 25 parts by weight of wax with respect to 100 parts by weight of the base resin, and the wax content in the resin fine particles is larger than the wax content in the core toner. The toner for developing electrostatic images according to any one of the above.