JP2002156780A - Electrostatic charge image developing toner, method for producing the same, and method for fixing the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerized toner of superior hot-offsetting resistance property, having proper OHP(overhead projector) transparency and superior electrostatic chargeability. SOLUTION: In the electrostatic charge image developing toner obtained by sticking or fixing fine resin particles on particle agglomerates containing at least primary polymer particles, the degree of crosslinking of the fine resin particles is 1-80% with respect to the THF-insoluble component, and the toner contains a wax having melting point in the ronge of 30-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge developing toner used in an electrophotographic copying machine and a printer. More specifically, the present invention relates to a toner for developing an electrostatic image, which is manufactured by an emulsion polymerization aggregation method.

[0002]

2. Description of the Related Art Toners for electrostatic development, which have been widely and generally used in electrophotography, include a styrene / acrylate copolymer, a colorant such as carbon black or a pigment, a charge controlling agent and / or a magnetic material. Has been produced by melt-kneading a mixture containing, and then pulverizing and classifying. However, the melt kneading /
The conventional toner obtained by the pulverization method has a limit in controlling the particle size of the toner, and it is difficult to produce a toner having an average particle size of substantially 10 μm or less, particularly 8 μm or less with a high yield, and will be used in electrophotography in future. It was not enough to achieve the required high resolution.

In order to achieve low-temperature fixability, a method has been proposed in which a wax having a low softening point is blended into a toner during kneading. However, in a kneading / pulverizing method, a blend of about 5% is limited. Thus, a toner exhibiting sufficient low-temperature fixing performance and sufficient OHP transparency could not be obtained. JP-A-63-186253 proposes a method for producing a toner by an emulsion polymerization / aggregation method in order to overcome the problem of particle size control and achieve high resolution. However, even in this method, the amount of wax that can be introduced in the aggregation step is limited, and a sufficient improvement effect on low-temperature fixability has not been obtained. Also, Japanese Patent Application Laid-Open No.
No. 012 proposes a method for producing a toner by an emulsion polymerization / aggregation method comprising crosslinked primary particles in order to suppress the gloss of an image. However, in this method, sufficient OHP transparency cannot be obtained, and OHP transparency is not sufficient.

[0004]

SUMMARY OF THE INVENTION The present invention overcomes the drawbacks of conventional electrostatic image developing toners and provides a new toner which satisfies high resolution, low-temperature fixability, offset resistance and OHP transparency. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that a coaggregated toner using wax fine particles and polymer primary particles, or a polymer obtained by emulsion polymerization using wax fine particles as a seed. It has been found that the above-mentioned problems can be solved by using an aggregated toner using the aggregated primary particles and encapsulating the particle aggregate with resin fine particles having a degree of crosslinking of 5 to 70% of a tetrahydrofuran-insoluble content. Reached.

That is, the gist of the present invention is to provide a toner for developing an electrostatic image in which resin fine particles are adhered or fixed to a particle aggregate containing at least polymer primary particles, wherein the resin fine particles have a tetrahydrofuran-insoluble content of 5%. ７０70%, and the toner contains a wax having a melting point of 30 to 100 ° C.

Another gist of the present invention is to provide a toner for developing an electrostatic image, in which resin fine particles are adhered or fixed to a particle aggregate containing at least polymer primary particles, wherein the content of the tetrahydrofuran-insoluble portion of the toner is 5% to 20%. %, And the toner contains a wax having a melting point of 30 to 100 ° C.

[0008] Another gist of the present invention is that a primary particle of a polymer obtained by emulsion polymerization and a wax having a melting point of 30 to 100 ° C are coaggregated to form a particle aggregate having an average volume particle size of 3 to 10 µm,
The present invention relates to a method for producing a toner for developing an electrostatic image, characterized by adhering or fixing resin fine particles obtained by polymerizing a monomer mixture containing at least one polyfunctional monomer to the particle aggregate by an emulsion polymerization method.

Another gist of the present invention is that the melting point is 30 to 100.
The polymer particles are polymerized by an emulsion polymerization method using wax fine particles at a temperature of 0 ° C. as a seed to form polymer primary particles, which are aggregated to form particle aggregates having an average volume particle size of 3 to 10 μm, and the particle aggregate has at least one polyfunctional monomer. A method for producing a toner for developing an electrostatic image, characterized by adhering or fixing resin fine particles obtained by polymerizing a monomer mixture containing the above by an emulsion polymerization method.

Another aspect of the present invention resides in a method for fixing a toner, characterized in that the toner for developing an electrostatic image is fixed by a fixing device having a fixing roller having a rubber hardness of 90 or more.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The toner for developing an electrostatic image of the present invention produces polymer primary particles by an emulsion polymerization method, the polymer primary particles, a colorant, and if necessary, other additives such as a charge controlling agent and a fluidizing agent. Into a particle aggregate by adhering or fixing resin fine particles to the particle aggregate. The toner contains a low melting point wax, and the resin fine particles covering the particle aggregate are crosslinked. It is characterized by the following.

The wax used in the present invention has a melting point of 3
As long as the wax has a low melting point of 0 to 100 ° C., any known wax can be used. Specifically, low-molecular-weight polyethylene, low-molecular-weight polypropylene, olefin-based wax such as copolymerized polyethylene, paraffin wax, Behenyl behenate, montanic acid ester, ester wax having a long chain aliphatic group such as stearyl stearate, vegetable wax such as hydrogenated castor oil carnauba wax, ketone having a long chain alkyl group such as distearyl ketone, alkyl group Higher fatty acids such as silicone, stearic acid and the like, long-chain fatty acid alcohols, fatty acid polyhydric alcohols such as pentaerythritol, and partial esters thereof, higher fatty acid amides such as oleic amide and stearamide, and saccharides of aliphatic carboxylic acids Esters and the like are exemplified.

The melting point of the wax used is 30 to 100.
° C, preferably 40 ° C or higher, more preferably 50 ° C or higher, and preferably 90 ° C or lower, more preferably 80 ° C or lower. If the melting point exceeds 100 ° C., the effect of low-temperature fixing becomes poor. Still further, an ester wax having a long-chain aliphatic group is preferable, and among the ester waxes, those having 10 to 30 carbon atoms in the aliphatic group are more preferable,
Further, the number of carbon atoms in the entire molecule is particularly preferably from 20 to 60. These waxes may be used not only alone but also in a mixture. Particularly when an ester-based wax is used, it is preferable to use a mixture of a plurality of esters having different carbon numbers.

The wax fine particles used in the present invention are obtained by emulsifying the above wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants and nonionic surfactants.

In the present invention, these wax fine particles are used for resin seed polymerization. Alternatively, the above wax fine particles are coagulated with primary polymer particles and colorant fine particles described below.

Specific examples of the cationic surfactant used as the emulsifier include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.

Further, specific examples of the nonionic surfactant include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, Decanoyl sucrose and the like.

The weight average particle diameter of the wax fine particles is 0.0
It is preferably at least 1 μm, more preferably at least 0.03 μm, particularly preferably at least 0.05 μm. Further, it is preferably 3 μm or less, more preferably 1 μm or less, and 0.8 μm or less.
The following are particularly preferred. If the average particle size of the wax emulsion is larger than 3 μm, the average particle size of the polymer particles obtained by seed polymerization becomes too large, which is not suitable for applications requiring high resolution as a toner.
When the average particle size of the emulsion is smaller than 0.01 μm, the wax content in the polymer primary particles after the seed polymerization becomes too low, and the effect of the wax becomes poor.

The wax is usually made of a binder resin 100
1 part by weight or more, preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and usually 40 parts by weight or less, preferably 35 parts by weight or less, more preferably 30 parts by weight or less based on parts by weight. . If the amount of the wax having a melting point of 30 to 100 ° C. is within the above range, a wax having a melting point of 100 ° C. or more may be used in common. In addition, a component other than the wax, for example, a pigment, a charge control agent, and the like may be simultaneously used as a seed without departing from the spirit of the present invention.

In the seed emulsion polymerization in the presence of the wax emulsion, a monomer having a polar group (a monomer having a Bronsted acidic group or a monomer having a basic functional group) and other monomers are sequentially added. The polymerization proceeds in the wax-containing emulsion. At this time, the monomers may be added separately, or a plurality of monomers may be mixed in advance and added. Further, the monomer composition can be changed during the addition of the monomer. Further, the monomer may be added as it is, or may be added as an emulsified liquid which is previously mixed and adjusted with water or a surfactant.

In carrying out the seed emulsion polymerization,
A certain amount of an emulsifier may be added to the wax emulsion. The timing of adding the polymerization initiator may be before adding the monomer, simultaneously adding the monomer, or after adding the monomer, or may be a combination of these adding methods. The polymer primary particles obtained as described above are polymer particles substantially containing wax, and have a morphology of a core-shell type, a phase separation type,
It may take any form such as an occlusion type, or a mixture of these forms. Particularly preferred is the core-shell type.

Examples of the monomer having a Bronsted acidic group used in the present invention include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and cinnamic acid, and sulfonic acid groups such as sulfonated styrene. And a monomer having a sulfonamide group such as styrenesulfonamide. Examples of the monomer having a Bronsted basic group include monomers having an amino group such as aminostyrene, dimethylaminoethyl acrylate, and diethylaminoethyl methacrylate, and monomers containing a nitrogen-containing heterocycle such as vinylpyridine.

Other comonomers include styrene,
Methyl styrene, chlorostyrene, dichlorostyrene,
styrenes such as p-tert-butylstyrene, pn-butylstyrene, pn-nonylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate,
N-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethyl hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethylhexyl methacrylate, (Meth) acrylic acid esters, such as (meth) acrylic acid esters, acrylamides, and methacrylic acid dimethylamides. Among them, styrene, butyl acrylate and the like are particularly preferable.

The polymer primary particles used in the present invention may be formed into a crosslinked resin by using a polyfunctional monomer described below. However, in order to make the tetrahydrofuran-insoluble content of the toner 7 to 20%, the polymer primary particles are used. The content of tetrahydrofuran insoluble is preferably 0 to 15%.

In the present invention, primary particles of the colorant are aggregated simultaneously with the primary particles of the polymer and the wax particles, or simultaneously with the primary particles of the polymer containing the wax, to form associated particles to form the toner core material. The coloring agent used in the above may be any of an inorganic pigment, an organic pigment, an organic dye, or a combination thereof.

Specific examples of the colorant used in the primary particles of the colorant include carbon black, aniline blue,
Any known dyes and pigments such as phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes and condensed azo dyes Can be used alone or as a mixture. In the case of a full-color toner, it is preferable to use benzidine yellow, monoazo-based and condensed azo-based dyes and pigments for yellow, quinacridone and monoazo-based dyes and pigments for magenta, and phthalocyanine blue for cyan, respectively. The colorant is used in an amount of preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight of the binder resin.

These colorants are also emulsified in water in the presence of an emulsifier and are used in the form of an emulsion. The average particle size is preferably 0.01 to 3 μm. Any known charge control agent can be used alone or in combination. Considering the color toner adaptability (the charge control agent itself is colorless or light color and there is no color hindrance to the toner), a quaternary ammonium salt compound is used as the positive charge, and chromium of salicylic acid or alkyl salicylic acid is used as the negative charge. , Zinc, aluminum and other metal salts, metal complexes and benzylic acid metal salts, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4'-methylenebis [2- [N- (4- Chlorophenyl) amide]
-3-hydroxynaphthalene] and the like. The amount used may be determined depending on the desired charge amount of the toner, but is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more, and particularly preferably 1 part by weight, based on 100 parts by weight of the binder resin. that's all,
Further, the amount is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, particularly preferably 5 parts by weight or less.

In the present invention, as a method for incorporating a charge control agent into a toner, when obtaining polymer primary particles, the charge control agent may be used alone or as a seed simultaneously with wax, or the charge control agent may be used as a monomer or wax. Dissolved or dispersed in water, or used to aggregate the primary particles of the charge control agent simultaneously with the primary particles of the polymer to form a particle aggregate, which may be used as a toner, but before or after the step of attaching or fixing the resin fine particles. At the same time or after the step, it is preferable to attach or fix the primary particles of the charge control agent. In this case, the charge control agent is also used as an emulsion (primary particles of the charge control agent) having an average particle size of 0.01 to 3 μm in water.

Next, a feature of the present invention is that the above-mentioned particle aggregate containing at least polymerized primary particles is further coated (adhered or fixed) with resin fine particles having a degree of crosslinking of 5 to 70% of a tetrahydrofuran-insoluble matter, thereby forming toner particles. Is formed. As the resin fine particles, preferably, the volume average particle size is 0.02 μm or more, more preferably 0.05 μm
And preferably 2 μm or less.
Those having a size of 5 μm or less and obtained by polymerizing monomers similar to the monomers used for the above-mentioned polymer primary particles can be used. Then, at least one polyfunctional monomer is used as a copolymerization component of the resin fine particles so that the degree of crosslinking is 5 to 70% as a tetrahydrofuran insoluble content. Here, the tetrahydrofuran-insoluble matter is an index indicating the degree of crosslinking, and the larger the tetrahydrofuran-insoluble matter, the higher the degree of crosslinking of the resin. The content insoluble in tetrahydrofuran is preferably at least 7%,
It is more preferably at least 10%. In addition, preferably 6
0% or less, more preferably 50% or less,
Control that way. If the degree of cross-linking is too low, offset tends to occur, and if it is too high, the OHP transparency decreases.

The polyfunctional monomer used in the present invention means a monomer having at least two ethylenic double bonds having radical polymerizability in a molecule. Examples of the polyfunctional monomer used in the present invention include divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, and neopentyl glycol acrylate. And the like. It is also possible to use a monomer having a reactive group in the pendant group, for example, glycidyl methacrylate, methylolacrylamide, acrolein and the like. Of these, divinylbenzene and hexanediol diacrylate are preferred. The blending ratio of such a polyfunctional monomer in the monomer mixture is preferably at least 0.005% by weight, more preferably at least 0.1% by weight, particularly preferably at least 0.3% by weight. It is preferably at most 5% by weight, more preferably at most 3% by weight, particularly preferably at most 1% by weight.

The resin fine particles are dispersed in water or a liquid mainly composed of water using an emulsifier (the above-mentioned surfactant) and used as an emulsion. It is preferable to use resin fine particles obtained by an emulsion polymerization method. Resin fine particles obtained by emulsion polymerization using the above-mentioned wax fine particles as seeds are also suitably used.

The amount of the resin fine particles to be coated is preferably at least 1 part by weight, more preferably at least 3 parts by weight, particularly preferably at least 5 parts by weight, based on 100 parts by weight of the resin constituting the particle aggregate. It is preferably at most 20 parts by weight, more preferably at most 15 parts by weight, particularly preferably at most 12 parts by weight.

Prior to coating the particle aggregate with the resin fine particles, the particle aggregate may be fused at a temperature equal to or higher than the glass transition point of the primary polymer particles. Further, the toner of the present invention can be used together with an additive such as a fluidizing agent, if necessary. Specific examples of such a fluidizing agent include fine particles such as hydrophobic silica, titanium oxide, and aluminum oxide. Powder can be mentioned, and is usually 0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.
3 parts by weight are used.

Further, the toner of the present invention may contain an inorganic additive such as magnetite, ferrite, cerium oxide, strontium titanate, or conductive titania; a resistance modifier such as styrene resin or acrylic resin; a lubricant; Used as an additive. The amount of these additives used may be appropriately selected depending on the desired performance, and usually about 0.05 to 10 parts by weight per 100 parts by weight of the binder resin is suitable.

In the toner of the present invention produced using the above-mentioned components, a crosslinked resin is used as the resin fine particles for coating the particle aggregates, but the polymer primary particles and the wax are almost dissolved in tetrahydrofuran, In addition, the polymer primary particles are also preferably substantially soluble because of using a low degree of crosslinking, while the colorant is usually not dissolved in tetrahydrofuran, and the charge control agent may or may not be dissolved in tetrahydrofuran. Since the charge control agent is used in a small proportion with respect to other components, when these factors are taken into account, when the tetrahydrofuran insoluble content of the toner is measured, approximately 7 to 20% of the toner becomes insoluble content. The content of the toner insoluble in tetrahydrofuran is preferably 8% or more, more preferably 10% or more, and preferably 18% or less, more preferably 16% or less.

The toner for electrostatic charge development of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, a known carrier such as a magnetic substance such as iron powder, magnetite powder, or ferrite powder, or a mono or magnetic carrier having a resin coating on the surface thereof can be used as the carrier.
As the coating resin for the resin-coated carrier, generally known styrene resins, acrylic resins, styrene-acryl copolymer resins, silicone resins, modified silicone resins, fluororesins, and mixtures thereof can be used. Next, a preferred fixing device that can be used for fixing the toner of the present invention will be described. As shown in FIG. 1, the fixing device typically includes an upper fixing member and a lower fixing member, and has a heating device inside the upper or lower fixing member. In the fixing device shown here, an upper fixing member (a member on which the recording paper surface on which the toner is placed is in contact) is a fixing roller.
The lower fixing member is a pressure roller 72.

The fixing roller 71 has an elastic layer 71b on a cylindrical metal core 71c having a heating source inside, and further has a coating layer 71a thereon. The material of the cylindrical core metal is not particularly limited, but metals such as aluminum, iron, and stainless steel are usually used. As the heat source provided inside the metal core, any heat source conventionally used for the fixing roller may be used, and for example, a heater lamp or the like can be used.

As the material of the elastic layer, a known rubber material can be used as long as it has heat resistance enough to withstand continuous use at the fixing temperature, and a material having good heat conductivity is preferable. Specifically, for example, silicone rubber such as RTV silicone, LTV silicone, HTV silicone and the like, fluorine rubber, butadiene rubber, isoprene rubber and the like can be mentioned.
If the hardness of the fixing roller is to be reduced, an elastic body made of a relatively soft material such as silicone rubber may be provided. If the hardness of the fixing roller is to be increased, the elasticity of a relatively hard material may be used. The body may be provided or the elastic body may not be provided.

The thickness of the coating layer is usually at least 10 μm, preferably at least 12 μm, and usually at most 200 μm, preferably at most 100 μm, particularly preferably at most 50 μm.
m or less. Preferred fluororesins used for the coating layer include polytetrafluoroethylene (PTFE) resin or tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA) resin paint or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) Resins. The coating layer can be used by mixing with other resins compatible with these fluororesins.
% By weight, more preferably 70% by weight or more.

Further, an elastic body, a coating layer, and a heater may be provided on the pressure roller side. In a preferred embodiment of the present invention, the fixing roller 71 and the pressure roller 72
Is preferably 3 mm or more, more preferably 4 mm or more, and preferably 30 mm or more.
mm or less, more preferably 20 mm or less. Also,
The speed at which the recording paper passes through the nip is preferably 70 mm / sec or more, more preferably 100 mm / sec or more, and particularly preferably 120 mm / sec or more. Although there is no particular upper limit of the speed, it is usually 500 mm / or less due to the limitation of the apparatus.

The toner of the present invention uses a crosslinked resin as the resin fine particles for coating the toner core material (particle aggregate), and therefore has a relatively hard structure on the surface of the toner. Therefore, the case where the hardness of the fixing roller is relatively hard is more effective in fixing the toner of the present invention. Specifically, it is preferable that the rubber hardness of the fixing roller surface is 90 or more. Here, the rubber hardness indicates a rubber hardness measured in accordance with the Japan Rubber Association Standard SRIS 0101. The rubber hardness of the fixing roller surface is more preferably 92 or more, particularly preferably 94 or more.

[0042]

The present invention will be specifically described below with reference to examples. In the following examples, “parts” means “parts by weight”. The average particle size, molecular weight, glass transition point (Tg), fixing temperature width, and charge amount of the polymer particles were measured by the following methods.

Average particle size: Measured using LA-500 manufactured by Horiba, Microtrac UPA manufactured by Nikkiso Co., Ltd., or Coulter Counter Multisizer II (abbreviated as Coulter Counter) manufactured by Coulter. Weight average molecular weight: measured by gel permeation chromatography (GPC). (Solvent: THF, calibration curve: standard polystyrene) Glass transition point (Tg): DSC7 manufactured by PerkinElmer
Was measured by

The tetrahydrofuran-insoluble content indicating the degree of crosslinking was measured by adding 1 g of the toner to 50 g of tetrahydrofuran in 25 g.
The mixture was allowed to stand at 24 ° C. for 24 hours to dissolve, and the amount remaining after filtration (calculated by subtracting the amount of pigment) was determined. The melting point of the wax was measured at a heating rate of 10 ° C using DSC-20 (manufactured by Seiko).
/ min., and the peak temperature of the peak showing the maximum endotherm in the DSC curve was taken as the melting point of the wax.

Fixing temperature range: A recording sheet carrying an unfixed toner image is prepared, and the temperature of the heating roller (fixing roller) is set to 1
Change to 00-220 ° C and transport to fixing nip
The fixing state at the time of discharge was observed. A temperature region in which no offset occurred on the heating roller at the time of 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 fixing was evaluated without applying silicone oil, the fixing speed was 75 mm / sec and 19 mm / sec, and the nip width was 2.5 mm. The fixing roller is made of aluminum as a core metal and 50 μm-thick tetrafluoroethylene-perfluoroalkylvinyl ether copolymer (PFA) as a coating layer, and has no elastic layer. The rubber hardness of the fixing roller surface was 94.

The OHP transparency was evaluated using the above fixing roller, oilless, 19 mm / sec, nip width 2.5 mm, 180 ° C.
Is fixed on an OHP film under the conditions described above, and the transmittance of 480 nm and 620 nm is measured for cyan in a spectrophotometer,
700nm and 560nm transmittance, yellow 680nm and 400nm
The transmittance in nm was measured, and the difference was used as a value.

Charge: The toner is charged into a non-magnetic one-component developing tank (ColorPagePrestoN4 developing tank manufactured by Casio or Phaser550 developing tank manufactured by Kyushu Matsushita), and the roller is rotated a certain number of times. The amount of charge per unit weight was determined from the amount of charge and the weight of the sucked toner.

(Preparation of Wax Dispersion) As 100 parts of a wax dispersion, 30 parts of behenyl behenate was emulsified by applying high pressure shearing in the presence of 1.67 parts of sodium dodecylbenzenesulfonate, and the ester wax dispersion was obtained. Obtained. The solid content of the obtained dispersion is 30%, and LA
The average particle size measured at -500 was 340 nm (this is referred to as wax dispersion A).

As 100 parts of the wax dispersion, 30 parts of behenyl behenate was emulsified under high pressure shearing in the presence of 0.23 part of sodium dodecylbenzenesulfonate to obtain an ester wax dispersion. The solid content concentration of the obtained dispersion was 30%, and the average particle diameter measured by LA-500 was 400 nm (this is referred to as wax dispersion B).

68.33 parts of demineralized water and an ester mixture mainly composed of behenyl behenate (Unistar M-2222S
L, 30 parts of Nippon Yushi) and 1.67 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 66%), emulsified by applying high pressure shearing at 90 ° C., and ester wax. A dispersion was obtained. LA-50
The average particle size measured at 0 was 340 nm (this is referred to as wax fine particle dispersion C).

(Preparation of Polymer Primary Particle Dispersion) In a glass reactor equipped with a stirrer, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 35 parts of the following amount of wax dispersion A, 400 parts of demineralized water was charged and heated to 90 ° C. under a nitrogen stream. Thereafter, the following monomers, an aqueous emulsifier solution, and an initiator were added, and emulsion polymerization was performed for 6.5 hours.

[0052]

(Table 1) (Monomers) Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Octanethiol 0.38 parts (Emulsifier aqueous solution) 10% sodium dodecylbenzenesulfonate (S-DBS) aqueous solution 1 part Demineralized water 25 parts ( Initiator) 8% aqueous hydrogen peroxide solution 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts

After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight average molecular weight of the obtained polymer dispersion was 45,000, and the average particle diameter measured by UPA was 200 n.
m and Tg were 57 ° C. When a cross section of the obtained emulsion was observed with a TEM, it was observed that the wax was encapsulated in the resin (this is referred to as a polymer primary particle dispersion A). The THF insoluble content of the polymer primary particles was 0%.

A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion A, except that the wax dispersion B was used in place of the wax dispersion A and the monomers were changed as follows. The obtained polymer dispersion has a weight average molecular weight of 52,000 and an average particle diameter measured by UPA of 190 n.
m and Tg were 48 ° C. (This is referred to as polymer primary particle dispersion B). THF insoluble content of polymer primary particles is 0%
Met.

[0055]

[Table 2] (Monomers) 64 parts of styrene 36 parts of butyl acrylate 3 parts of acrylic acid 0.5 part of trichlorobromomethane

A milky white polymer dispersion was obtained in the same manner as in the polymer primary particle dispersion B except that the styrene and the butyl acrylate were changed to 67 parts and 33 parts, respectively, of the monomer components. The weight average molecular weight of the obtained polymer dispersion is 40,0.
00, average particle diameter measured by UPA is 190 nm, Tg
Was 51 ° C. (This is referred to as polymer primary particle dispersion C). The THF insoluble content of the polymer primary particles was 0%.

A milky white polymer dispersion was obtained in the same manner as the polymer primary particle dispersion B, except that the styrene and the butyl acrylate were changed to 72 parts and 28 parts among the monomer components, respectively. The weight average molecular weight of the obtained polymer dispersion was 43.0.
00, average particle diameter measured by UPA is 170 nm, Tg
Was 55 ° C. (This is referred to as polymer primary particle dispersion D). The THF insoluble content of the polymer primary particles was 0%.

Stirring device (three retreating blades), heating and cooling device,
35 parts of the wax dispersion C and 396 parts of demineralized water were charged into a reactor (volume: 3 liters, inner diameter: 150 mm) equipped with a concentrating device and each raw material / auxiliary charging device.
The temperature was raised to ° C., and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% aqueous ascorbic acid solution were added. Thereafter, a mixture of the monomer and emulsifier aqueous solution having the same composition as that used for the polymer primary particle dispersion A was added over 5 hours from the polymerization initiator, and the initiator aqueous solution was added over 6 hours from the start of polymerization,
Hold for another 30 minutes. After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight average molecular weight of the THF-soluble component of the polymer was 45,000, the average particle size measured by UPA was 200 nm, and the Tg was 57 ° C. (this is referred to as polymer primary particle dispersion E). The THF insoluble content of the polymer primary particles was 0%.

(Preparation of Resin Fine Particle Dispersion) Stirrer (3
Reactor equipped with a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device (volume: 2 liter, inner diameter: 1)
In 20 mm), 4.3 parts of a 15% neogen SC aqueous solution and 376 parts of demineralized water were charged, and the temperature was increased to 90 ° C. under a nitrogen stream.
1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Then, the following monomers
The mixture of the emulsifier aqueous solution was added over 5 hours from the polymerization initiator,
The initiator aqueous solution was added over 6 hours from the start of the polymerization, and the mixture was further maintained for 30 minutes.

[0060]

(Table 3) (Monomers) Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Bromotrichloromethane 0.5 parts 2-mercaptoethanol 0.01 parts Divinylbenzene 0.4 parts (Emulsifier aqueous solution) 15% Neogen SC aqueous solution 2.2 parts Demineralized water 25 parts (Initiator aqueous solution) 8% hydrogen peroxide aqueous solution 10.6 parts 8% ascorbic acid aqueous solution 10.6 parts

After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the THF-soluble component of the polymer is 98,000, and the average particle size measured by UPA is 150 n.
m and Tg were 65 ° C. (this is resin fine particle dispersion A). The THF insoluble content was 15%.

(Preparation of Colorant Fine Particle Dispersion) Deionized Water 65
To this part, 30 parts of Pigment Blue 15:30 and 5 parts of polyoxyethylene nonylphenyl ether were added and dispersed by a sand grinder mill to obtain a colorant fine particle dispersion. The solid content of the obtained dispersion is 35%,
The average particle size measured by PA was 150 nm. (This is referred to as colorant fine particle dispersion A)

Pigment Red 2 was added to 77.5 parts of demineralized water.
3820 parts and 2.5 parts of sodium dodecylbenzenesulfonate were added thereto, and subjected to a dispersion treatment with a sand grinder mill for 6 hours to obtain a colorant fine particle dispersion. The solid content concentration of the obtained dispersion was 20%, and the average particle size measured by UPA was 180 nm. (This is referred to as colorant fine particle dispersion B)

Pigment Yellow 74 is added to 73 parts of demineralized water.
20 parts and 7 parts of polyoxyethylene nonylphenyl ether were added, and the mixture was subjected to a dispersion treatment with a sand grinder mill for 6 hours to obtain a colorant fine particle dispersion. The solid content concentration of the obtained dispersion was 20%, and the average particle size measured by UPA was 300 nm. (This is referred to as colorant fine particle dispersion C)

Pigment Blue 15: 3 aqueous dispersion (E
P-700 Blue GA, manufactured by Dainichi Seika, solid content 35
%). The average particle size measured by UPA was 150 nm (this is referred to as colorant fine particle dispersion D).

(Preparation of Charge Control Agent Fine Particle Dispersion) In 76 parts of demineralized water, a charge control agent 4,4'-methylenebis [2-
The mixture was dispersed in a sand grinder mill in the presence of 20 parts of [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] and 4 parts of an alkyl lunaphthalene sulfonate to obtain a charge control agent fine particle dispersion. The solid content concentration of the obtained dispersion was 24%, and the average particle size measured by UPA was 200 nm. (This is referred to as a charge control agent fine particle dispersion A)

[0067]

[Table 4]

The above components were mixed in the following order. An aqueous solution of sodium dodecylbenzenesulfonate was added to the polymer primary particle dispersion A and mixed uniformly, and then the colorant fine particle dispersion A was added and uniformly mixed. An aqueous solution of aluminum sulfate was added at 30 ° C. while stirring the mixed dispersion thus obtained with an anchor blade equipped with baffles (0.6 part as a solid content). The average particle size of the mixed dispersion after the addition of the aqueous aluminum sulfate solution was 2 μm. Thereafter, with stirring, the temperature was raised to 55 ° C. and maintained for 1 hour, and further raised to 58 ° C. and maintained for 1 hour. Thereafter, the charge control agent fine particle dispersion A, the resin fine particle dispersion A, and an aqueous solution of aluminum sulfate (0.1 part as a solid content) were added in this order. After holding for 1.5 hours, a 10% S-DBS aqueous solution (3 parts as a solid content) was added, and then the temperature was raised to 95 ° C. and held for 4 hours. Thereafter, the mixture was cooled, filtered and washed with a Kiriyama funnel, and freeze-dried to obtain a toner (this is referred to as toner A).

To 100 parts of the toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (this is referred to as developing toner A). The volume average particle diameter of the obtained toner A measured by a Coulter counter is 7.5.
μm. Further, the ratio of the volume particle size of 5 μm or less is 1.6%, the ratio of the volume particle size of 15 μm or more is 0.2%, the ratio of the volume average particle size to the number average particle size is 1.1, and the particle size distribution is very high. It was narrow and good. The content of the toner insoluble in tetrahydrofuran was 15%.

When the fixing property of the developing toner A was evaluated, it was fixed at 180 to 220 ° C. at a fixing speed of 120 mm / sec, and fixed at 150 to 180 ° C. at a fixing speed of 30 mm / sec. OHP transparency was 65%. The charge amount of the toner A measured by ColorPagePrest was −10 μC / g, and the charge amount of the developing toner A was −20 μC / g.

Example 2 The procedure of Example 1 was repeated, except that the colorant particle dispersion A was changed to the colorant particle dispersion B.
Toner B and developing toner B were obtained. The volume average particle diameter of the toner B is 7.6 μm, the ratio of the volume particle diameter of 5 μm or less is 1.3%, and the ratio of the volume particle diameter of 15 μm or more is 0.2%. The ratio was 1.09 and the particle size distribution was very narrow and good. The content of the toner insoluble in tetrahydrofuran was 15%.

When the fixing property of the developing toner B was evaluated, the fixing temperature range was from 120 to 190 ° C., and the OHP transparency was 55%. The charge amount of the toner B measured by ColorPagePrest was −22 μC / g, and the charge amount of the developing toner B was −25 μC / g.

Example 3 The procedure of Example 1 was repeated, except that the colorant particle dispersion A was changed to the colorant particle dispersion C.
Toner C and developing toner C were obtained. The volume average particle diameter of the toner C is 7.4 μm, the ratio of 5 μm or less of the volume particle diameter is 1.5%, and the ratio of 15 μm or more is 0.2%. The ratio was 1.11 and the particle size distribution was very narrow and good. The content of the toner insoluble in tetrahydrofuran was 14%.

When the fixing property of the developing toner C was evaluated, it was fixed at a fixing temperature range of 130 to 200 ° C., and the OHP transparency was 60%. The charge amount of the toner C measured by ColorPagePrest was −5 μC / g, and the charge amount of the developing toner C was −20 μC / g.

[0075]

[Example 5] 100 parts of polymer primary particle dispersion B (as solid content) 21 parts of resin fine particle dispersion A (as solid content) 6.7 parts of colorant fine particle dispersion A (as solid content) 0.1 part of charge control agent fine particle dispersion (as solid content)

The above components were mixed in the following order. Colorant fine particle dispersion A was added to polymer primary particle dispersion B, and mixed uniformly. An aqueous NaCl solution was added at 20 ° C. while stirring the obtained mixed dispersion with an anchor blade (10 parts as a solid content). Thereafter, the temperature was raised to 45 ° C. and maintained for 1 hour while stirring, and further raised to 95 ° C. and maintained for 5 hours, and then cooled to obtain toner particles.

100 parts of the toner particles were charged and stirred in a glass reactor equipped with a stirring device, a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. Here, the charge control agent fine particle dispersion liquid A and the resin fine particle dispersion liquid A are added.
Hold at 5 ° C. for 2 hours. Thereafter, the mixture was cooled, filtered and washed with a Kiriyama funnel, and freeze-dried to obtain a toner (this is referred to as toner D).

To 100 parts of the toner, 0.6 part of silica having been subjected to a hydrophobic surface treatment was mixed and stirred to obtain a developing toner (this is referred to as developing toner D). The volume average particle diameter of the obtained toner D was 7.4 μm. The ratio of the volume average particle size to the number average particle size was 1.09, and the particle size distribution was very narrow and good. The content of the toner insoluble in tetrahydrofuran was 12%. When the fixing property of the developing toner D was evaluated, the fixing temperature range was 110 to 180 ° C.
The transparency was 70%. The charge amount of the developing toner D measured by Phaser was −24 μC / g.

Example 5 A toner E and a developing toner E were obtained in the same manner as in Example 4, except that the polymer primary particle dispersion B was changed to the polymer primary fine particle dispersion C. The volume average particle diameter of the toner E was 6.7 μm, the ratio of the volume average particle diameter to the number average particle diameter was 1.10, and the particle diameter distribution was very narrow and good. The tetrahydrofuran insoluble content of the toner was 18%. When the fixing property of the developing toner E was evaluated, the toner was fixed at 110 to 200 ° C. at a fixing speed of 120 mm / sec.
er, the charge amount of the developing toner E is −25 μC /
g.

Example 6 Toner F was prepared in the same manner as in Example 4 except that polymer primary particle dispersion B was changed to polymer primary fine particle dispersion D and resin fine particle dispersion A was changed to 10 parts. Thus, a developing toner F was obtained. The volume average particle size of the toner F is 6.5 μm, and the ratio of the volume average particle size to the number average particle size is 1.09.
And the particle size distribution was very narrow and good. When the fixing property of the developing toner F was evaluated, the fixing temperature range was 100
The toner was fixed at １７０170 ° C., and the charge amount of the developing toner F measured by Phaser was −25 μC / g.

Comparative Example 1 A toner G and a developing toner G were obtained in the same manner as in Example 3 except that the resin fine particle dispersion A was not added. The volume average particle size of the toner G was 7.4 μm. The content of the toner insoluble in tetrahydrofuran was 8%. When the fixing property of the developing toner G was evaluated, the toner was fixed at a fixing temperature range of 150 to 160 ° C., and the OHP transparency was not measured because it was offset. ColorPagePrest
As a result, the toner G was not negatively charged. The charge amount of the developing toner G was −2 μC / g.

Comparative Example 2 A toner H and a developing toner H were obtained in the same manner as in Example 6, except that the resin fine particle dispersion A was not added. The volume average particle diameter of the toner H was 6.5 μm. The ratio between the volume average particle size and the number average particle size was 1.1. The content of the toner insoluble in tetrahydrofuran was 7%. When the fixing property of the developing toner H was evaluated, the fixing was performed at a fixing temperature range of 150 to 160 ° C., and the OHP transparency was offset, so that the measurement was not possible. As measured by Phaser, the developing toner H was not negatively charged.

Comparative Example 3 A toner J and a developing toner J were obtained in the same manner as in Example 1, except that divinylbenzene was not used in preparing the resin fine particle dispersion. The volume average particle diameter of the toner J was 6.5 μm. The ratio between the volume average particle size and the number average particle size was 1.02. The content of the toner insoluble in tetrahydrofuran was 5.5%. When the fixing property of the developing toner J was evaluated, the fixing temperature range was 170 to 180 ° C. As measured by Phaser, the charge amount of the developing toner J was −19 μC / g.
Met.

[0084]

[Example 6] Polymer primary particle dispersion E 90 parts (as solid content) Resin fine particle dispersion A 10 parts (as solid content) Colorant fine particle dispersion D 6.7 parts (as solid content) Charge Control Agent Fine Particle Dispersion A 2 parts (as solids) 15% Neogen SC aqueous solution 0.5 part (as solids)

Using each of the above components, a toner was manufactured according to the following procedure. A polymer primary particle dispersion and a 15% aqueous solution of neogen SC were charged into a reactor (volume: 1 liter, anchor wing with baffle), mixed uniformly, and then a colorant fine particle dispersion was added and uniformly mixed. While stirring the obtained mixed dispersion, an aqueous solution of aluminum sulfate was added dropwise (0.6 part as a solid content). Thereafter, with stirring, the temperature was raised to 55 ° C. over 20 minutes and maintained for 1 hour, and further raised to 58 ° C. over 5 minutes and maintained for 1 hour. The charge control agent fine particle dispersion, the resin fine particle dispersion, and the aqueous solution of aluminum sulfate (0.1 part as a solid content) were added in this order, and the mixture was maintained for one and a half hours, and then heated to 65 ° C. over 25 minutes. After adding a 15% aqueous solution of neogen SC (3 parts as a solid content), the temperature was raised to 95 ° C. over 30 minutes and maintained for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (this is referred to as toner K). To 100 parts of this toner, 0.6 part of silica subjected to hydrophobic surface treatment was mixed and stirred to obtain a developing toner (developing toner K).

The volume average particle diameter of the developing toner K measured by a Coulter counter was 7.5 μm, and the ratio of the volume average particle diameter to the number average particle diameter was 1.1. The 50% circularity was 0.98. The fixing property of the developing toner K is a fixing speed of 75 mm.
/ S (nip width 2.5 mm), fixing was performed at 180 to 220 ° C., and at a fixing speed of 19 mm / s (nip width 2.5 mm), fixing was performed at 150 to 180 ° C. The THF insoluble content of the toner was 15%. The charge amount of the toner K is −10 μm
C / g and the charge amount of the developing toner K were −20 μC / g.

[0087]

According to the present invention, it is possible to provide a polymerized toner which has a sufficient non-offset region even in the heating roller fixing method, has a good OHP transparency and is excellent in chargeability. Further, the polymerized toner of the present invention has a small particle size and a sharp particle size distribution, and is suitable for forming a high-resolution image.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing details of a fixing device used in the present invention.

[Explanation of symbols]

 71 Upper fixing member (fixing roller) 72 Lower fixing member (pressure roller) 71a Coating layer 71b Elastic layer 71c Cylindrical core 71d Heater lamp T Toner P Recording paper

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/08 381 384

Claims (13)

[Claims] 1. An electrostatic image developing toner comprising resin fine particles adhered or fixed to a particle aggregate containing at least polymer primary particles, wherein the resin fine particles have a tetrahydrofuran-insoluble content of 5% to 70%, and , Toner has a melting point of 3
A toner for developing an electrostatic image, comprising a wax at 0 to 100 ° C. 2. The electrostatic charge image developing toner according to claim 1, wherein wax-free resin fine particles are adhered or fixed to the surface of the particle aggregate containing the wax fine particles. 3. The toner for developing an electrostatic image according to claim 1, wherein the monomer constituting the polymer primary particles has a Bronsted acidic group or a Bronsted basic group. 4. The electrostatic image developing toner according to claim 1, wherein the melting point of the wax is 40 to 90 ° C. 5. The toner for developing an electrostatic image according to claim 1, wherein the wax is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the binder resin. 6. The electrostatic image developing toner according to claim 1, wherein the resin fine particles have a tetrahydrofuran insoluble content of 7 to 30%. 7. The particle aggregate according to claim 1, wherein the charge control agent is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the binder resin in the particles. 6. The toner for developing an electrostatic image according to any one of 6. 8. A toner for developing an electrostatic image, wherein resin fine particles are attached or fixed to a particle aggregate containing at least polymer primary particles, wherein the toner has a tetrahydrofuran-insoluble content of 5% to 20%, and Has a melting point of 30-1
A toner for developing an electrostatic charge image, comprising a wax at 00 ° C. 9. The electrostatic image developing toner according to claim 1, wherein the primary polymer particles have a tetrahydrofuran insoluble content of 0 to 15%. 10. The polymer primary particles obtained by emulsion polymerization and a wax having a melting point of 30 to 100 ° C. are coaggregated to form a particle aggregate having an average volume particle size of 3 to 10 μm, and the particle aggregate has at least one kind of particles. A method for producing a toner for developing an electrostatic image, comprising adhering or fixing resin fine particles obtained by polymerizing a monomer mixture containing a polyfunctional monomer by an emulsion polymerization method. 11. Polymerization by emulsion polymerization using wax fine particles having a melting point of 30 to 100 ° C. as seeds to form polymer primary particles, which are aggregated to form particle aggregates having an average volume particle diameter of 3 to 10 μm. A method for producing a toner for developing an electrostatic charge image, comprising adhering or fixing resin fine particles obtained by polymerizing a monomer mixture containing at least one polyfunctional monomer to an aggregate by an emulsion polymerization method. 12. The toner according to claim 10, wherein the proportion of the polyfunctional monomer in the polymerization of the monomer mixture by an emulsion polymerization method is 1 to 30% by weight based on all the monomers. Production method. 13. A method for fixing a toner according to claim 1, wherein the toner for developing an electrostatic image according to claim 1 is fixed by a fixing device having a fixing roller having a rubber hardness of 90 or more.