JP2002196525A - Electrostatic charge image developing toner and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having anti-offsetting property, low temperature fixability, transparency to OHP(overhead projector) and high resolution and to provide a method for producing the toner. SOLUTION: In the electrostatic charge image developing toner obtained by agglomerating at least primary particles of a polymer, at least three wax compounds are contained and the proportion of each of the wax compounds does not exceed 45 wt.% of the amount of the entire wax.

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 image, which is manufactured by an emulsion polymerization aggregation method.

[0002]

2. Description of the Related Art Toners for developing electrostatic images, which have been widely used in electrophotography, have been used in combination with a styrene / acrylate copolymer, a coloring agent such as carbon black or a pigment, a charge controlling agent and / or a magnetic material. It has been manufactured by melt-kneading a mixture containing a body with an extruder, followed by pulverization and classification. However, the conventional toner obtained by the above-described melt-kneading / pulverization method has a limit in controlling the particle size of the toner, and it is necessary to produce a toner having an average particle size of substantially 12 μm or less, particularly 8 μm or less with a high yield. However, it cannot be said that it is sufficient to achieve the high resolution required for electrophotography in the future. Further, in order to achieve low-temperature fixability, a method of blending a wax having a low softening point into a toner during kneading has been proposed. However, in a kneading / pulverizing method, a blend of about 5% is a limit.
A toner exhibiting sufficient low-temperature fixing performance and sufficient OHP transparency could not be obtained.

[0003] JP-A-8-50368 discloses a toner in which ester waxes containing 50 to 95% of an ester compound having the same total carbon number are contained in an ester wax.
Specifically, the toner described in the publication is a toner obtained by a suspension polymerization method, and although the fixing property is improved, it is not always satisfactory in terms of the particle size distribution and the like.

[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. And a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems, the present inventors have used a mixture of three or more compounds as a wax of a toner obtained by an emulsion polymerization coagulation method and have a comparative purity. The present inventors have found that the above-mentioned problems can be solved by using an object which is extremely low, and have reached the present invention. That is, the gist of the present invention is that in a toner for developing an electrostatic image obtained by aggregating at least polymer primary particles, the toner contains at least three kinds of wax compounds, and the ratio of each of the wax compounds is based on the entire wax. In any case, the toner does not exceed 45% by weight. Another gist of the present invention is to polymerize a monomer mixture containing at least one polyfunctional monomer by an emulsion polymerization method to form polymer primary particles, and coaggregate with wax fine particles to obtain a volume average particle size of 3 to 1
In the method for producing a toner for developing an electrostatic charge image having a particle aggregate of 2 μm, the wax fine particles contain at least three kinds of wax compounds, and the ratio of each of the wax compounds does not exceed 45% by weight based on the whole wax. The present invention is also directed to a method for producing a toner for developing an electrostatic image.

[0006] Another aspect of the present invention provides at least one aspect.
A monomer mixture containing various kinds of polyfunctional monomers is polymerized by an emulsion polymerization method using at least wax fine particles as seeds to form polymer primary particles, which are aggregated to form particle aggregates having a volume average particle diameter of 3 to 12 μm. A method for producing a toner for image development, characterized in that the wax fine particles contain at least three kinds of wax compounds, and the proportion of each of the wax compounds does not exceed 45% by weight with respect to the whole wax. The present invention resides in a method for producing a toner for use in a computer.

[0007]

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 thereto, characterized in that at least three kinds of wax compounds are used in combination as a wax. As the wax compound used in the present invention, any of known wax compounds conventionally used in toner waxes can be used, and specific examples thereof include olefins such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymerized polyethylene. Wax, 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 And higher fatty acids such as silicone, stearic acid and the like, long-chain fatty acid alcohols, higher fatty acid amides such as oleic acid amide and stearic acid amide, and saccharide esters of aliphatic carboxylic acids. At least three kinds of wax compounds to be used in combination can be selected from the known waxes described above, and in this case, any of the wax compounds is blended so as not to exceed 45% by weight based on the whole wax. It is necessary to. Further, it is preferable that any of the wax compounds is blended so as not to exceed 40% by weight based on the whole wax.

At least one of the wax compounds used in combination is preferably a carboxylic acid ester of a monohydric or polyhydric alcohol. The wax compound having the largest content is more preferably an alkanoic acid ester of a monohydric or polyhydric alcohol, and particularly preferably an alkanoic acid alkyl ester. When the wax compound having the highest content is an alkanoic acid alkyl ester, the second largest amount of the wax compound may be another alkanoic acid alkyl ester or a polyhydric alcohol alkanoic acid ester. preferable. The type of the wax compound used in combination is 4
More than one kind is preferred, and five or more kinds are more preferred. The upper limit of the type of the wax compound used in combination is not particularly limited, but is preferably 50 or less in terms of production.

In addition, the sum of two wax compounds having a large blending amount among at least three kinds of wax compounds is preferably not more than 88% by weight, more preferably not more than 85% by weight, based on the whole wax. Is more preferable, and particularly preferably 80% by weight or less. Further, the melting point of the wax compound having the largest amount is preferably 30 ° C. or higher, more preferably 40 ° C. or higher.
C. or less, more preferably 90.degree. C. or less. It is particularly preferable that the melting points of the two types of wax compounds having a large amount are 40 ° C. or more and 90 ° C. or less. 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 seed polymerization of a resin. Alternatively, the above-mentioned wax fine particles are co-aggregated with a polymer primary particle dispersion described below and colorant fine particles. Specific examples of the cationic surfactant used as an 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, sodium lauryl sulfate and the like. Specific examples of nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, and monodecanoyl sulfate. Sugars and the like.
The weight average particle diameter of the wax fine particles is preferably 0.01 μm or more, more preferably 0.03 μm or more, and 0.05 μm or more.
Particularly preferably, it is at least μm. Further, it is preferably at most 3 μm, more preferably at most 1 μm, particularly preferably at most 0.8 μm. When the average particle diameter of the wax fine particles is larger than 3 μm, the average particle diameter of the polymer particles obtained by the seed polymerization becomes too large, which is not suitable for applications requiring high resolution as a toner. When the average particle diameter of the fine particles is smaller than 0.01 μm, it is difficult to prepare a dispersion.

In preparing the wax fine particles, there is no particular limitation on the method of blending at least three types of waxes. For example, the wax fine particles may be prepared for each of the three types of wax compounds and then mixed. The wax fine particles may be prepared after mixing various kinds of wax compounds in advance. Of these, the latter is preferred. Wax is usually
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 100 parts by weight of the binder resin. Used in

As a method for incorporating a wax into a toner, specifically, for example, a method of coaggregating wax fine particles and polymer-free primary particles containing no wax, a method of subjecting a monomer mixture to seed emulsion polymerization of the wax fine particles as a seed, Is produced by preparing polymer primary particles containing the polymer and aggregating the particles. In the toner of the present invention, it is preferable to use wax fine particles as seeds in consideration of the dispersibility of the wax in the toner.

Further, a component other than the wax, such as a pigment, a charge controlling agent, etc., may be used as a seed at the same time as long as the gist of the present invention is not deviated. When seed emulsion polymerization is performed in the presence of wax fine particles, a monomer having a polar group (a monomer having a Bronsted acidic group or a monomer having a basic functional group) is successively used.
And the other monomers, the polymerization proceeds in the emulsion containing the fine wax particles.
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, an emulsifier may be added to an emulsion containing a certain amount of wax. 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 their morphology is any of core-shell type, phase separation type, occlusion type, etc. It may be in the form 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 monomers having a sulfonic acid group such as sulfonated styrene. , Etc.

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. it can. Other comonomers include styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert.
Styrenes such as -butylstyrene, p-butylstyrene, p-nonylstyrene, etc., methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methacrylic acid (Meth) such as methyl, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethylhexyl methacrylate, etc.
Acrylamides such as acrylates and dimethylamide acrylate can be mentioned. Of these, styrene and butyl acrylate are particularly preferred. In the present invention, the resin is cross-linked by using a polyfunctional monomer as a polymerization component together with the above-described monomer, and the degree of cross-linking of the polymer primary particles is adjusted so that the tetrahydrofuran-insoluble content is 1 to 8
It is preferable to control the amount to be 0% by weight, particularly 15 to 70% by weight. The content of tetrahydrofuran insolubles is more preferably 20% by weight or more, and particularly preferably 25% by weight or more.
% By weight or more. Further, the content is more preferably 65% by weight or less. 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.

If the degree of crosslinking is too low, offset tends to occur, while if it is too high, the OHP transparency tends to decrease.
In addition, the colorant described below is not usually dissolved in tetrahydrofuran, and the charge control agent described later may or may not be dissolved in tetrahydrofuran.However, the charge control agent is generally used for other components. The ratio is small. The ratio of the tetrahydrofuran insoluble component may be determined in consideration of these factors. The content of the tetrahydrofuran-insoluble component in the toner of the present invention is preferably 12 to 90% by weight, and more preferably 15 to 80% by weight.
% By weight is preferred. The content of tetrahydrofuran insolubles is more preferably at least 20% by weight, particularly preferably at least 45% by weight. 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. In the present invention, the colorant primary particles are aggregated simultaneously with the polymer primary particles and the wax particles, or simultaneously with the wax-encapsulated polymer primary particles to form a particle aggregate, which is used as the toner core material. The coloring agent to be used may be any of inorganic pigments, organic pigments, organic dyes, or a combination thereof. Specific examples of the colorant used in the colorant primary particles include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine-based dyes and pigments, chrome yellow, quinacridone, benzidine yellow, rose bengal, and triallyl. Any known dyes and pigments such as methane dyes, monoazo dyes, disazo dyes and condensed azo dyes can be used alone or in combination. 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. Can be These colorants are also emulsified in water in the presence of an emulsifier and used in the form of an emulsion, but those having an average particle size of 0.01 to 3 μm are preferably used. 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, metal salts and metal complexes with aluminum, metal salts of benzylic acid, metal complexes, amide compounds,
Preferred are phenol compounds, naphthol compounds, phenolamide compounds, and hydroxynaphthalene compounds such as 4,4'-methylenebis [2- [N- (4-chlorophenyl) amido] -3-hydroxynaphthalene]. 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. The amount is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, and particularly preferably 5 parts by weight or less. In the present invention, as a method of including a charge control agent in 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 dissolved or dissolved in a monomer or wax. Used as dispersed or agglomerated 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 simultaneously with the step of attaching or fixing resin fine particles or After the process, it is preferable to attach or fix the primary particles of the charge control agent. In this case, the charge control agent also has an average particle size in water of 0.01 to 3 μm.
(Primary particles of charge control agent). Next, in the toner of the present invention, a particle aggregate containing primary polymerized particles may be used as it is or may be used as a toner by adding an external additive, but may be further coated (adhered or fixed) with resin fine particles. It is preferred to form toner particles.

When the resin fine particles are coated, the appearance of the charge control agent, wax and the like on the toner surface is suppressed, so that the chargeability is improved and the contamination of the apparatus can be reduced. The resin fine particles for coating the toner core material preferably have a volume average particle size of 0.02 μm or more, more preferably 0.05 μm or more, and preferably 2 μm or more.
m or less, more preferably 1.5 μm or less, and those obtained by polymerizing monomers similar to the monomers used for the above-mentioned polymer primary particles can be used. 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 80 parts by weight, more preferably at most 40 parts by weight, particularly preferably at most 20 parts by weight.

Prior to coating the particle aggregate with the resin fine particles or after coating the resin fine particles, the particle aggregate may be fused at a temperature equal to or higher than the glass transition point of the polymer primary particles. In a preferred embodiment of the present invention, the above-described polymer primary particles, colorant primary particles, and, if necessary, charge control agent fine particles, wax fine particles, and other internal additives, respectively, are emulsified to form an emulsion, Co-aggregate to form particle aggregates. Among the components that perform aggregation, the charge control agent dispersion may be added during the aggregation step or may be added after the aggregation step.

In the coagulation step, there are 1) a method of performing coagulation by heating, and 2) a method of performing coagulation by adding an electrolyte. When performing aggregation by heating, the aggregation temperature is specifically in the temperature range of 5 ° C. to Tg (where Tg is the glass transition temperature of the polymer primary particles), and Tg−10.
C. to Tg-5 C. are preferred. Within the above temperature range, the toner can be aggregated to a preferable toner particle size without using an electrolyte.

Further, in the case of performing aggregation by heating, when performing the aging step subsequent to the aggregation step, the aggregation step and the aging step are performed continuously, and the boundary may be ambiguous. If there is a step of maintaining the temperature in a temperature range of −20 ° C. to Tg for at least 30 minutes, this is regarded as a flocculation step. The aggregation temperature is preferably maintained at a predetermined temperature for at least 30 minutes to obtain toner particles having a desired particle size. The temperature may be raised at a constant rate up to a predetermined temperature, or may be raised stepwise. The retention time was Tg-2
30 minutes or more and 8 hours or less are preferable in the range of 0 ° C. to Tg,
One hour or more and less than 4 hours are more preferable. By doing so, a toner having a small particle size and a sharp particle size distribution can be obtained. Further, as an electrolyte in the case of performing aggregation by adding an electrolyte to the mixed dispersion, any of an organic salt and an inorganic salt may be used, but a monovalent or divalent or higher polyvalent metal salt is preferably used. . Specifically, NaCl, KCl, LiCl, Na ₂ SO ₄ , K
₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO
₄ , CaSO ₄ , ZnSO ₄ , Al ₂ (SO ₄ ) ₃ , Fe
₂ (SO ₄ ) ₃ , CH ₃ COONa, C ₆ H ₅ SO ₃ Na and the like.

The amount of the electrolyte to be added varies depending on the type of the electrolyte, but is usually 0.05 to 25 parts by weight based on 100 parts by weight of the solid component of the mixed dispersion. Preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight
Parts by weight. When the amount of the electrolyte added is significantly smaller than the above range, the progress of the agglutination reaction is slowed down and the
Problems tend to occur, such as fine powder having a particle size of μm or less remaining, or an average particle size of the obtained aggregated particles being 3 μm or less.
On the other hand, when the amount of the electrolyte added is significantly larger than the above range, agglomeration tends to occur rapidly and is difficult to control, and coarse particles of 25 μm or more are mixed in the obtained agglomerated particles, and the shape of the agglomerated body is not smooth. It tends to cause problems such as becoming fixed-shaped objects.

When coagulation is performed by adding an electrolyte, the coagulation temperature is preferably in the range of 5 ° C. to Tg. Further, in order to increase the stability of the aggregated particles (toner particles) obtained by the aggregation, Tg to Tg + 80 ° C., preferably Tg + 20
It is preferable to add a ripening step of causing fusion between aggregated particles in a temperature range of from 0 ° C. to Tg + 80 ° C. and at a temperature not higher than the softening point of the primary polymer particles. By adding the aging step, the shape of the toner particles can be made nearly spherical, and the shape can be controlled. This aging step is usually for 1 hour to 24 hours, preferably 1 hour to 10 hours, particularly preferably 2 hours to 10 hours.
As the reaction tank used in the aggregation step, a stirring tank type reaction tank is usually used, and a substantially cylindrical or substantially spherical shape is preferably used. When the reaction tank is substantially cylindrical, the shape of the bottom surface is not particularly limited, but an ordinary substantially arc-shaped one is preferably used.

In order to improve the stirring efficiency, the volume of the mixed dispersion is preferably ３ or less of the volume of the reaction tank,
/ 3 or less is more preferable. Also, if the volume of the mixed dispersion is extremely small compared to the volume of the reaction solution, bubbling is intense, thickening is increased, coarse powder particles are likely to be generated, and depending on the shape of the stirring blade, stirring may not be performed. This ratio is preferably 1/10 or more, more preferably 1/5 or more, since the production efficiency is also lowered. As the stirring blade used in the coagulation step, conventionally known and commercially available stirring blades having various shapes can be used.

Commercially available stirring blades include, for example, anchor blades, full zone blades (manufactured by Shinko Pantech Co., Ltd.), Sun Meller blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max Blend blades (manufactured by Sumitomo Heavy Industries, Ltd.), and Hi-F mixers. Stirring blades such as blades (manufactured by Soken Chemical Co., Ltd.) and double helical ribbon blades (manufactured by Shinko Pantech Co., Ltd.) can be mentioned. Further, a baffle may be provided in the stirring tank.

Usually, a suitable stirring blade is selected from these stirring blades depending on the viscosity and other physical properties of the reaction solution, the reaction form, the shape and size of the reaction tank, and the like. Specifically, a double helical ribbon wing or an anchor wing is used. Further, the toner of the present invention can be used together with an additive such as a fluidizing agent if necessary after the aggregation step. Specific examples of such a fluidizing agent include hydrophobic silica, titanium oxide, Fine powders such as aluminum oxide can be given, and preferably at least 0.01 part by weight, more preferably at least 0.1 part by weight, and preferably at most 5 parts by weight, based on 100 parts by weight of the binder resin. It is preferably used in a range of 3 parts by weight or less. Further, the toner of the present invention is magnetite, ferrite, cerium oxide, strontium titanate, inorganic fine powder such as conductive titania, a styrene resin, a resistance regulator such as an acrylic resin or a lubricant as an internal additive or an external additive. Used. 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. The toner for developing an electrostatic image 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. Further, when the toner of the present invention is used in a high-resolution printer or copier, the toner has a relatively small particle size,
It is preferable that the particle size distribution is sharp because the charge amount of each toner particle tends to be uniform.

The volume average particle diameter of the toner of the present invention is good.
It is preferably 3 to 12 μm, more preferably 4 to 10 μm.
μm, particularly preferably 5 to 9 μm. Also,
As an index representing the particle size distribution, a volume average particle size (D_V) And individual
Number average particle size (D_N) And the ratio (D _V/ D_N)
And D_V/ D_NIs preferably 1.24 or less, and 1.22
The following is more preferable, and the value of 1.20 or less is particularly preferable. D
_V/ D_NIs 1 and the diameters of all particles are equal.
And is advantageous for high-resolution image formation.
However, it is extremely difficult to obtain a particle size distribution that actually becomes 1.
And therefore difficult from a manufacturing point of view._V/ D_NIs 1.
03 or more, preferably 1.05 or more. Change
If too much fine powder (toner with too small a particle) is
And scattering into the device increases, and the charge amount distribution deteriorates.
Tendency, and too much coarse powder (too large particle size toner)
And the charge amount distribution tends to be worse, resulting in higher resolution images.
Not suitable for forming. For example, the volume average of the toner
When the particle size is 7 to 10 μm, the particle size of 5 μm or less
Toner is preferably 10% by weight or less of the whole toner.
More preferably, the content is 5% by weight or less. Also one
5% by weight or less of toner having a particle size of 5 μm or more
It is more preferably at most 3% by weight. This
The particle size is relatively small and the particle size distribution is sharp
When manufacturing a certain toner, the emulsion polymerization aggregation of the present invention is used.
Method by suspension polymerization, kneading and powdering
This is advantageous as compared with the crushing method.

The 50% circularity of the toner is 0.95.
The above is preferable, and 0.96 or more is more preferable. 50%
The maximum value of the degree of circularity is 1, which means that the toner is substantially spherical. However, since it is difficult to obtain such a toner, from the viewpoint of manufacturing, it is preferably 0. 99 or less. Although the reason why the toner of the present invention exerts an excellent effect is not necessarily clear, when a toner is produced by an emulsion polymerization aggregation method, since a wax component is relatively uniformly dispersed in a state of fine particles in toner particles, A wax component having a broader melting point width, that is, a mixture and a lower purity, gives a good wax discharge from the toner at the time of fixing even when the fixing temperature changes, and therefore, the fixing property is low. It is estimated that it will be good.

[0030]

The present invention will be specifically described below with reference to examples. In the following examples, “parts” means “parts by weight”
“Average particle size” or “average particle size” means “volume average particle size” unless otherwise specified. Also, the average particle size,
The weight average molecular weight, glass transition point (Tg), 50% circularity, fixing temperature range, OHP permeability, charge amount, blocking resistance, tetrahydrofuran (THF) insoluble matter, and melting point of wax were measured by the following methods, respectively. .

Ratio of toner particles having a volume average particle size of 5 μm or less and 15 μm or more: Measured by LA-500 manufactured by Horiba, Microtrac UPA manufactured by Nikkiso Co., Ltd., or Coulter Counter Multisizer II manufactured by Coulter (abbreviated as Coulter Counter). did. Weight average molecular weight (Mw): measured by gel permeation chromatography (GPC) (apparatus: Tosoh GPC apparatus HLC-8020, column: Polym
er Laboratory PL-gel Mix
ed-B 10 μm, solvent: tetrahydrofuran, 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).

50% circularity: The toner was measured with a flow particle image analyzer FPIA-2000 manufactured by Sysmex Corporation, and the circularity corresponding to the cumulative particle size value at 50% of the value obtained from the following equation was used. Circularity = perimeter of circle having the same area as particle projection area / perimeter of particle projection image Fixing temperature width: Prepare recording paper carrying an unfixed toner image, and adjust the surface temperature of heating roller from 100 ° C. to 220 ° C. The fixing state was observed when the sheet was conveyed to the fixing nip and discharged. 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 vulcanizable 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. The evaluation was performed without applying silicone oil and the nip width was 4 mm. The fixing speed was 120 mm / s or 30 mm / s.

Since the evaluation range is 100 ° C. to 220 ° C., if the upper limit of the fixing temperature is described as 220 ° C., the true upper limit of the fixing temperature may be higher. OHP transparency: an unfixed OHP sheet-like toner image is fixed without applying silicone oil using the above fixing roller, and a spectrophotometer (U-3210 manufactured by Hitachi, Ltd.) is used.
Then, the transmittance is measured in a wavelength range of 400 to 700 nm,
Difference between the transmittance at the wavelength with the highest transmittance (maximum transmittance (%)) and the transmittance at the wavelength with the lowest transmittance (minimum transmittance (%)) (maximum transmittance−minimum transmittance)
Used as value. The fixing conditions are as follows: a fixing speed of 30 mm /
s, 180 ° C.

Amount of charge: The toner was put into a non-magnetic one-component developing layer (a developing layer of ColorPagePresto N4 manufactured by Casio), and after a certain number of rotations of the roller, the toner on the roller was sucked and the amount of charge was sucked. The charge amount per unit volume was determined from the toner weight. Blocking resistance: 10 g of toner for development is placed in a cylindrical container, a load of 20 g is applied, the toner is left in an environment of 50 ° C. for 5 hours, the toner is taken out of the container, and a load is applied from above to determine the degree of aggregation. confirmed. ：: No aggregation △: Aggregated but collapsed by a light load ×: Aggregated and not collapsed even when a load was applied Tetrahydrofuran (THF) insolubles: Measurement of toners, polymer primary particles, and tetrahydrofuran insolubles in resin fine particles Means adding 1 g of a sample to 50 g of tetrahydrofuran and adding
The solution was allowed to stand still at 24 ° C. for 24 hours, and filtered using 10 g of Celite. The solvent in the filtrate was distilled off to determine the tetrahydrofuran-soluble content, and the tetrahydrofuran-insoluble content was calculated by subtracting from 1 g.

Melting point of wax: Measurement was performed at a heating rate of 10 ° C./min using a DSC-20 manufactured by Seiko Instruments Inc., and the temperature at the peak of the peak showing the maximum endotherm in the DSC curve was taken as the melting point of the wax. Example 1 (Wax Dispersion-1) 68.33 parts of demineralized water, an ester mixture mainly composed of behenyl behenate (Unistar M-
2222SL, manufactured by NOF Corporation. 30 parts of a 7: 3 mixture of ester mixture composed mainly of stearyl stearate (melting point: 70 ° C.) and stearyl stearate (manufactured by NOF Corporation, melting point: 65 ° C.), sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., effective (66% of component) 1.67
Were mixed and emulsified by applying high-pressure shearing at 90 ° C. to obtain a dispersion of ester wax fine particles. The average particle size of the ester wax fine particles measured by LA-500 was 340 nm.

The wax is behenyl behenate of about 38.
%, Stearyl stearate about 15%, C ₄₂ H ₈₄ O ₂ component about 13%, C ₄₀ H ₈₀ O ₂ component about 12%, other about 22%
% Mixture. (Polymer primary particle dispersion-1) A wax dispersion is placed in a reactor (volume: 60 liters, inner diameter: 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries. -128 parts, 1.2 parts of a 15% Neogen SC aqueous solution, and 393 parts of deionized water were charged, and 90 parts of the mixture were added under a nitrogen stream.
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 following monomers and an aqueous solution of an emulsifier was added over 5 hours from the start of the polymerization, and an aqueous solution of the initiator was added over 6 hours from the start of the polymerization.

[0039]

[Table 1] [Monomers] Styrene 79 parts (5530 g) Butyl acrylate 21 parts Acrylic acid 3 parts Octanethiol 0.38 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.9 parts [Emulsifier aqueous solution] 15 % Neogen SC aqueous solution 1 part Demineralized water 25 parts [Initiator aqueous solution] 8% Hydrogen peroxide aqueous solution 9 parts 8% Ascorbic acid aqueous solution 9 parts After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion. The THF insoluble content of the polymer primary particles is 52% by weight,
The weight-average molecular weight of the THF-soluble component is 119,000,
The average particle size measured in A was 189 nm, and Tg was 57 ° C. (Resin Fine Particle Dispersion-1) 15 parts were placed in a reactor (volume: 60 liters, inner diameter: 400 nm) equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries.
% Neogen SC aqueous solution 5 parts, deionized water 372 parts,
The temperature was raised to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added.

Thereafter, the following mixture of the monomers 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.

[0041]

[Monomers] Styrene 88 parts (6160 g) Butyl acrylate 12 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.4 parts [Emulsifier aqueous solution] 15% Neogen SC aqueous solution 2.5 parts Demineralized water 24 parts [Initiator aqueous solution] 8% Hydrogen peroxide aqueous solution 9 parts 8% Ascorbic acid aqueous solution 9 parts After completion of the polymerization reaction, the mixture was cooled to obtain a milky white resin fine particle dispersion. The resin fine particles had a THF-insoluble content of 15% by weight, a weight-average molecular weight of the THF-soluble component of 54,000, an average particle size measured by UPA of 83 nm, and a Tg of 85 ° C. (Colorant Fine Particle Dispersion-1) Pigment Blue 15: 3
Aqueous dispersion (EP-700 Blue GA, manufactured by Dainichi Seika, solid content: 35%) The average particle size measured by UPA was 150 nm. (Charge Control Agent Fine Particle Dispersion-1) 4,4'-Methylenebis [2- [N- (4-chlorophenyl) amide] -3-
[Hydroxynaphthalene] 20 parts, alkylnaphthalenesulfonate 4 parts and demineralized water 76 parts were dispersed in a sand grinder mill to obtain a charge control agent fine particle dispersion liquid-1. U
The average particle size measured by PA was 200 nm.

[0042]

5. Production of toner for development-1 Polymer primary particle dispersion-1 104 parts (71 g: as solid content) Resin fine particle dispersion-1 6 parts (as solid content) Colorant fine particle dispersion-1 7 parts (as solid content) Charge control agent fine particle dispersion liquid-1 part (as solid content) 15% aqueous solution of neogen SC 0.5 part (as solid content) Manufactured.

In a reactor (volume: 1 liter, anchor blade with baffle), polymer primary particle dispersion and 15% neogen S
C aqueous solution was charged and uniformly mixed, 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). Then, with stirring, the temperature was raised to 51 ° C. over 20 minutes, held for 1 hour, and further increased to 58 ° C. over 6 minutes.
The temperature was raised to ° C. and maintained for 1 hour. The charge control agent fine particle dispersion liquid, the resin fine particle dispersion liquid, and the aluminum sulfate aqueous solution (0.07 part as solid content) were added in this order, and 60 minutes were added over 10 minutes.
The temperature was raised to ° C. and maintained for 30 minutes. After adding 15% neogen SC aqueous solution (3 parts as solid content), 9
The temperature was raised to 5 ° C. and maintained for 3.5 hours. Thereafter, the mixture is cooled, filtered, washed with water, and dried to form a toner (toner-1).
I got

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-1). Evaluation of Toner-1 The THF-insoluble content of the developing toner is 33% by weight, the volume average particle size by a Coulter counter is 7.2 μm, the ratio of the volume particle size of 5 μm or less is 3.5% by weight, and the ratio of 15 μm or more is 0%. 0.5% by weight, and the ratio of the volume average particle diameter to the number average particle diameter was 1.12. The 50% circularity was 0.97.

The fixing property of the developing toner-1 is determined by the fixing speed 1
At 20 mm / S, fixing was performed at 170 to 220 ° C., and at a fixing speed of 30 mm / S, fixing was performed at 130 to 220 ° C. OHP
The permeability was 70%. The charge amount of toner-1 is -7 μC
/ G, the charge amount of the developing toner-1 was -15 μC / g. The blocking resistance was ○. [Example-2] (Wax dispersion liquid-2) The one prepared in the same manner as the wax dispersion liquid-1 was used. The average particle size of the ester wax fine particles measured by LA-500 was 340 nm. (Polymer primary particle dispersion liquid-2) Wax dispersion liquid in a reactor (volume: 60 liters, inner diameter: 400 mm) equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. -228 parts, 1.2 parts of a 15% neogen SC aqueous solution, and 393 parts of deionized water were charged, and 90 parts of the mixture were added under a nitrogen stream.
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 following monomers and an aqueous solution of an emulsifier was added over 5 hours from the start of the polymerization, and an aqueous solution of the initiator was added over 6 hours from the start of the polymerization, and the mixture was further held for 30 minutes.

[0047]

[Table 4] [Monomers] Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Bromotrichloromethane 0.45 parts 2-mercaptoethanol 0.011 parts Hexanediol diacrylate 0.9 parts [Emulsifier aqueous solution] 15% Neogen SC aqueous solution 1 part Demineralized water 25 parts [Initiator aqueous solution] 8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion. The THF-insoluble content of the polymer was 60% by weight, the weight-average molecular weight of the THF-soluble component was 148,000, the average particle size measured by UPA was 207 nm, and the Tg was 55 ° C. (Resin Particle Dispersion-2) The same as Resin Particle Dispersion-1 was used. (Colorant Fine Particle Dispersion-2) Pigment Yellow 74
20 parts, 7 parts of polyoxyethylene alkylphenyl ether and 73 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion liquid-2. The average particle size measured by UPA was 211 nm. (Charge Control Agent Fine Particle Dispersion-2) The same as Charge Control Agent Fine Particle Dispersion-1 was used.

[0048]

Table 5 Production of toner for development-2 Polymer primary particle dispersion-2 105 parts (as solid content) Resin fine particle dispersion-1 5 parts (as solid content) Colorant fine particle dispersion-2 6.7 parts (As solid content) 12 parts of charge control agent fine particle dispersion liquid (as solid content) Using each of the above components, a toner was produced by the following procedure.

The polymer primary particle dispersion and the colorant fine particle dispersion were charged into a reactor (volume: 1 liter, anchor blade with baffle) and mixed uniformly. While stirring the obtained mixed dispersion, an aqueous solution of aluminum sulfate was added dropwise (0.6 part as a solid content). Then, with stirring for 25 minutes 5
The temperature was raised to 1 ° C. and maintained for 1 hour, and then 59 ° C. over 8 minutes.
And kept for 40 minutes. Charge control agent fine particle dispersion,
A resin fine particle dispersion and an aqueous solution of aluminum sulfate (0.07 part as solids) were added in this order, and the temperature was raised to 61 ° C. over 15 minutes and maintained for 30 minutes. After adding a 15% aqueous solution of Neogen SC (3.8 parts as a solid content), the temperature was raised to 96 ° C. over 30 minutes and maintained for 4 hours. Thereafter, the mixture is cooled, filtered, washed with water, and dried to form a toner (toner-2).
I got 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-2). Evaluation of Toner-2 The THF-insoluble content of the developing toner-2 is 55% by weight, the volume average particle size by a Coulter counter is 7.5 μm, the ratio of the volume particle size of 5 μm or less is 1.6% by weight, and the ratio of 15 μm or more. Was 0.7% by weight, and the ratio of the volume average particle size to the number average particle size was 1.14. The 50% circularity was 0.96.

The fixing property of the developing toner-2 is as follows.
At 20 mm / S, the image was fixed at 150 to 220 ° C, and at a fixing speed of 30 mm / S, the image was fixed at 130 to 220 ° C. The charge amount of the toner-2 was -4 .mu.C / g, and the charge amount of the developing toner-2 was -3 .mu.C / g. OHP permeability is 65%
And the blocking resistance was 性. [Example-3] (Wax dispersion-3) The same wax dispersion-1 was used. (Polymer Primary Particle Dispersion-3) Polymer Primary Particle Dispersion-
The same as 1 was used. (Resin Fine Particle Dispersion-3) The same as Resin Fine Particle Dispersion-1 was used. (Colorant Fine Particle Dispersion-3) Pigment Red 238
20 parts of the compound of the following formula (A), 2.5 parts of an alkylbenzene sulfonate, and 77.5 parts of demineralized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. U
The average particle size measured by PA was 181 nm.

[0051]

Embedded image

(Charge Control Agent Fine Particle Dispersion-3) The same as Charge Control Agent Fine Particle Dispersion-1 was used.

[0053]

Table 6 Production of toner for development-3 Polymer primary particle dispersion-1 104 parts (as solid content) Resin fine particle dispersion-1 6 parts (as solid content) Colorant fine particle dispersion-3 6.7 parts (As solid content) Charge control agent fine particle dispersion liquid-1 part (as solid content) 15% aqueous solution of neogen SC 0.65 part (as solid content) Using each of the above components, a toner was produced by the following procedure. .

In a reactor (volume: 1 liter, anchor blade with baffle), polymer primary particle dispersion and 15% neogen S
C aqueous solution was charged and uniformly mixed, 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 (0.8 part as a solid content). Then, with stirring, the temperature was raised to 51 ° C. over 15 minutes and held for 1 hour, and then 59 minutes over 6 minutes.
The temperature was raised to ° C. and maintained for 20 minutes. A charge control agent fine particle dispersion, a resin fine particle dispersion, and an aqueous solution of aluminum sulfate (0.09 part as solid content) were added in this order, and the mixture was kept at 59 ° C. for 20 minutes. 15% Neogen SC aqueous solution (3.
7 parts) and heated to 95 ° C. over 25 minutes,
Further, a 15% aqueous solution of Neogen SC (0.7% as solid content)
Parts) and maintained for 3.5 hours. Then cool down,
Filtration, washing with water, and drying make the toner (toner
3) was obtained.

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-3). Evaluation of Toner-3 The THF-insoluble content of the developing toner is 48% by weight, the volume average particle diameter by a Coulter counter is 7.8 μm, the ratio of the volume particle diameter of 5 μm or less is 2.1% by weight, and the ratio of 15 μm or more. Was 2.1% by weight, and the ratio between the volume average particle diameter and the number average particle diameter was 1.15. The 50% circularity was 0.97.

The fixing property of the developing toner-3 is as follows.
At 20 mm / S, fixing was performed at 160 to 220 ° C., and at a fixing speed of 30 mm / S, fixing was performed at 120 to 220 ° C. The charge amount of Toner-3 was -17 [mu] C / g, and the charge amount of Toner 3 for development was -17 [mu] C / g. The OHP permeability is 7
0%, and the blocking resistance was ○. Example 4 (Wax Dispersion-4) The same wax dispersion-1 was used. (Polymer primary particle dispersion-4) Polymer primary particle dispersion-
It was manufactured in the same amount and operation as in Example 2.

The THF insoluble content of the polymer was 60% by weight, the weight average molecular weight of the THF soluble component was 152,000,
The average particle diameter measured by UPA is 200 nm, Tg is 53
° C. (Colorant Particle Dispersion-4) The same as Colorant Dispersion-3 was used. (Charge Control Agent Fine Particle Dispersion-4) The same as Charge Control Agent Fine Particle Dispersion-1 was used.

[0058]

Table 7 Production of toner for development-4 Polymer primary particle dispersion-4 110 parts (as solid content) Colorant fine particle dispersion-3 6.7 parts (as solid content) Charge control agent fine particle dispersion-1 2 parts (as solid content) 15% aqueous solution of Neogen SC 0.65 parts (as solid content) Using each of the above components, a toner was produced by the following procedure.

In a reactor (volume: 1 liter, anchor blade with baffle), dispersion of polymer primary particles and 15% neogen S
C aqueous solution was charged and uniformly mixed, 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 (0.8 part as a solid content). Thereafter, the temperature was raised to 55 ° C. over 23 minutes with stirring, maintained for 1 hour, and further increased to 60 ° C. for 6 minutes.
The temperature was raised to ° C. and maintained for 25 minutes. The dispersion liquid of the charge control agent fine particles was added, and the mixture was kept at 59 ° C. for 30 minutes. 15% Neogen S
After the addition of the C aqueous solution (4 parts as a solid content), the temperature was raised to 96 ° C. over 28 minutes and maintained for 5 hours. Then cool down,
Filtration, washing with water, and drying make the toner (toner
4) was obtained.

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-4). Evaluation of Toner-4 The THF-insoluble content of the toner 4 for development is 60% by weight, the volume average particle size by a Coulter counter is 8.2 μm, the ratio of the volume particle size of 5 μm or less is 1.1% by weight, and the ratio of 15 μm or more. Was 1.8% by weight, and the ratio of the volume average particle diameter to the number average particle diameter was 1.15. The 50% circularity was 0.94.

The fixing property of the developing toner-4 is as follows.
At 20 mm / S, the image was fixed at 180-220 ° C, and at a fixing speed of 30 mm / S, the image was fixed at 150-210 ° C. The charge amount of the toner-4 was -20 .mu.C / g, and the charge amount of the developing toner-4 was -15 .mu.C / g. OHP permeability is 6
The blocking resistance was 5%. Comparative Example 1 (Wax Dispersion-5) 68.33 parts of demineralized water, an ester mixture mainly composed of behenyl behenate (Unistar M-
2222SL) 30 parts, sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Dai-ichi Kogyo Seiyaku, active ingredient 6)
(6%) was mixed and emulsified by applying high-pressure shear at 90 ° C. to obtain an ester wax dispersion. LA-500
Was 340 nm. (Polymer Primary Particle Dispersion-5) Reactor (3 liter capacity, 150 m inner diameter) equipped with a stirrer (three retreating blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device
m) was charged with 735 parts of a wax dispersion and 396 parts of demineralized water, heated to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 0.6 parts of an 8% aqueous ascorbic acid solution were added. Was added.

Thereafter, a mixture of the following monomers and an aqueous solution of an emulsifier was added over 5 hours from the start of the polymerization, and an aqueous solution of the initiator was added over 6 hours from the start of the polymerization.

[0063]

[Table 8] [Monomers] Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Octanethiol 0.38 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.7 parts [Emulsifier aqueous solution] 15% Neogen SC Aqueous solution 1 part Demineralized water 25 parts [Initiator aqueous solution] 8% aqueous hydrogen peroxide 9 parts 8% ascorbic acid aqueous solution 9 parts After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion. The THF-insoluble content of the polymer was 25% by weight, the weight-average molecular weight of the THF-soluble content was 98,000, the average particle size measured by UPA was 188 nm, and the Tg was 57 ° C. (Resin Particle Dispersion-5) A reactor (2 liters, 120 mm inner diameter) equipped with a stirrer (three retreating blades), a heating / cooling device, a concentrating device, and a device for charging each raw material / auxiliary material was used.
4.3 parts of a 5% neogen SC aqueous solution and 376 parts of demineralized water were charged, and the temperature was increased to 90 ° C. under a nitrogen stream, and 1.6 parts of an 8% aqueous hydrogen peroxide solution and 1.6 parts of an 8% ascorbic acid aqueous solution were added. Was added.

Thereafter, the following mixture of the monomers 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.

[0065]

[Table 9] [Monomers] Styrene 88 parts Butyl acrylate 12 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 24 parts [Initiator aqueous solution] 8% aqueous hydrogen peroxide 9 parts 8% ascorbic acid aqueous solution 9 parts After completion of the polymerization reaction, the mixture was cooled to obtain a milky white resin fine particle dispersion. The resin fine particles had a THF-insoluble content of 20% by weight, a weight-average molecular weight of the THF-soluble content of 111,000, an average particle size measured by UPA of 121 nm, and a Tg of 86 ° C. (Colorant Fine Particle Dispersion-5) The same as Colorant Fine Particle Dispersion-3 was used. (Charge Control Agent Fine Particle Dispersion-5) The same as Charge Control Agent Fine Particle Dispersion-1 was used.

[0066]

Table 10 Preparation of toner for development-5 Polymer primary particle dispersion liquid-599 parts (as solid content) Resin fine particle dispersion liquid-5 11 parts (as solid content) Colorant fine particle dispersion liquid-3 6.7 parts (As solid content) Charge control agent fine particle dispersion liquid-1 part (as solid content) 15% aqueous solution of neogen SC 0.65 part (as solid content) Using each of the above components, a toner was produced by the following procedure. .

In a reactor (volume: 1 liter, anchor blade with baffle), polymer primary particle dispersion and 15% neogen S
C aqueous solution was charged and uniformly mixed, 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 (0.8 part as a solid content). Thereafter, while stirring, the temperature was raised to 55 ° C. over 25 minutes and maintained for 1 hour, and the charge control agent fine particle dispersion was added, and the temperature was raised to 57 ° C. over 2 minutes. The resin fine particle dispersion was added and kept at 57 ° C. for 35 minutes. After adding 15% Neogen SC aqueous solution (4 parts as solid content), 40
The temperature was raised to 95 ° C. over a period of minutes and maintained for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner (toner-5).

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred to obtain a developing toner (developing toner-5). Evaluation of Toner-5 The THF-insoluble content of the developing toner-5 is 30% by weight, the volume average particle size by a Coulter counter is 7.3 μm, the ratio of the volume particle size of 5 μm or less is 1.4% by weight, and the ratio of 15 μm or more. Was 0.3% by weight, and the ratio of the volume average particle diameter to the number average particle diameter was 1.11. The 50% circularity was 0.98.

The fixing property of the developing toner 5 is as follows.
At 20 mm / S, the image was fixed at 180 to 220 ° C., and at a fixing speed of 30 mm / S, the image was fixed at 150 to 180 ° C. The charge amount of the toner-5 was -8 .mu.C / g, and the charge amount of the developing toner-5 was -14 .mu.C / g. OHP permeability is 60
%, And the blocking resistance was 性.

[0070]

According to the present invention, it is possible to provide a toner which has achieved offset resistance, low-temperature fixability, OHP transparency, and high resolution, and a method for producing the same.

Claims (14)

[Claims] 1. An electrostatic image developing toner obtained by aggregating at least polymer primary particles, wherein the toner contains at least three kinds of wax compounds, and the ratio of each of the wax compounds is all relative to the entire wax. A toner for developing electrostatic images, wherein the toner content does not exceed 45% by weight. 2. An electrostatic image developing toner comprising resin fine particles adhered or fixed to a particle aggregate obtained by aggregating at least polymer primary particles.
The toner contains at least three types of wax compounds, and the content of each of the wax compounds is 45% by weight.
A toner for developing an electrostatic image, wherein 3. The polymer primary particles are obtained by emulsion polymerization using wax fine particles as seeds.
3. The toner for developing an electrostatic image according to item 1. 4. The toner for developing an electrostatic image according to claim 1, which is obtained by coaggregating primary particles of a polymer and fine particles of wax. 5. The electrostatic image developing toner according to claim 1, which has a volume average particle diameter of 3 to 12 μm. 6. The electrostatic image developing toner according to claim 1, wherein a monomer constituting the polymer primary particles has a Bronsted acidic group or a Bronsted basic group. 7. The toner according to claim 1, wherein the wax compound is contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of the binder resin. 8. The toner for developing an electrostatic image according to claim 1, wherein the primary polymer particles have a tetrahydrofuran-insoluble content of 15 to 70% by weight. 9. The monomer constituting the polymer primary particles,
The polyfunctional monomer is 1 to 30% by weight.
The toner for developing electrostatic images according to any one of the above. 10. The wax compound having the highest content ratio among the wax compounds contained in the toner has a melting point of 3%.
The toner for developing an electrostatic image according to claim 1, wherein the temperature is 0 to 100 ° C. 11. 11. The toner for developing an electrostatic image according to claim 1, wherein the wax compound having the largest content among the wax compounds contained in the toner is an alkyl alkanoate compound. 12. A particle mixture having a volume average particle diameter of 3 to 12 μm by polymerizing a monomer mixture containing at least one polyfunctional monomer by an emulsion polymerization method to form polymer primary particles, and coaggregating with wax fine particles. The fine particles of wax are at least 3
A method for producing a toner for developing an electrostatic image, comprising: a wax compound of any kind, wherein the proportion of each of the wax compounds does not exceed 45% by weight based on the entire wax. 13. A polymer mixture comprising at least one polyfunctional monomer and polymerized by emulsion polymerization using at least wax microparticles as seeds to form polymer primary particles, which are aggregated to have a volume average particle diameter of 3 to 12 μm. In a method for producing a toner for developing an electrostatic charge image as a particle aggregate,
A method for producing a toner for developing an electrostatic image, wherein the wax fine particles contain at least three kinds of wax compounds, and the ratio of each of the wax compounds does not exceed 45% by weight based on the whole wax. 14. The method according to claim 12, wherein resin fine particles are adhered or fixed to the particle aggregate.
3. The method for producing a toner for developing an electrostatic charge image according to item 3.