JPH0511501A - Toner - Google Patents

Abstract

PURPOSE:To provide the toner which is an indefinite shaped toner having a uniform grain size distribution, can form images having a high resolution, is uniformly dispersed with coloring agents and a release agent used at need, is less dependent upon environment, is uniform in electrostatic charge quantity and has good fixing and cleaning properties. CONSTITUTION:This toner consists of the particles formed by polymerizing the compsn. consisting of polymerizable monomers, the coloring agents, the release agent used at need, and a charge control agent which can be selected as desired. The above-mentioned toner has 3.0 to 10.0mum average grain size, 1.1 to 1.5 dispersion degree and 1.3 to 3.0 indefinite shaped degree.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to toner used for developing an electrostatic latent image in electrostatic printing or the like.

[0002]

BACKGROUND OF THE INVENTION In one example of electrophotography, generally,
An electrostatic latent image is formed on the surface of the photoconductor by charging and imagewise exposure, and then this electrostatic latent image is developed with toner,
The obtained toner image is usually transferred to a recording material such as paper and then fixed by a heat roller fixing device or the like to form an image. . On the other hand, the toner remaining on the photoconductor after the transfer step is cleaned by a cleaning blade or the like and is used for forming the next image. On the other hand, as the toner constituting the developer, it is effective to use a toner having a small particle size obtained by a polymerization method in order to enhance the resolution and achieve high image quality. From this viewpoint, the following techniques have been conventionally proposed.

(1) In JP-A-62-266559, fine particles are once prepared, and a monomer system containing a polymerization initiator is added dropwise to a dispersion medium system. There has been proposed a toner which is unified to have an irregular shape. (2) JP-A-63-186253 proposes a toner in which primary particles made of a polymer having an acidic polar group or a basic polar group and secondary particles containing an arbitrary charge control agent are associated with each other. Has been done. The particle size of the primary particles is 0.05 to 0.5 μm, and the reaction temperature when obtaining the primary particles is 70 ° C. Furthermore, the particle size of the secondary particles is 0.5 to 5 μm, the reaction temperature for obtaining the secondary particles is 20 to 45 ° C., and the reaction time is 1 to 3 hours. The particle size of the associated particles is 3 to 25 μm, and the reaction temperature for obtaining the associated particles is from the glass transition point to the glass transition point + 2.
The temperature is set to 0 ° C. and the reaction time is set to 1 to 3 hours. (3) Japanese Patent Application Laid-Open No. 63-282749 proposes a toner containing an olefin resin emulsion when secondary particles are obtained. (4) Japanese Unexamined Patent Publication No. 2-511164 proposes a technique of preparing particles of 10 μm or less in size of 5 to 25 μm, and adding polyvinyl alcohol having a saponification degree of 60 to 85% to obtain a toner. Has been done. The reaction temperature of the primary particles is set to 65 ° C.

[0004]

However, in the above technique (1), it takes time to uniformly disperse the polymerization initiator,
Further, the particle size distribution is wide, and it is difficult to obtain an irregular toner having a small diameter. In the technique (2), hot offset is likely to occur and the fixability is poor. Further, since the solid content concentration is high and the manufacturing stability is poor, precise control of temperature and time is required. In the technique (3), it is difficult to uniformly disperse the colorant and the release agent, and a toner having a high degree of blackening cannot be obtained.
There is also a problem that hot offset is likely to occur. In the technique (4), the polyvinyl alcohol as the suspension stabilizer has a large environmental dependency of the charging property, and thus fog and toner scattering are likely to occur.

Therefore, the present invention has the following objects. (1) To provide an irregular toner having a small diameter that can form an image with high resolution. (2) To provide a toner having a uniform particle size distribution. (3) To provide a toner in which a colorant and a release agent are uniformly dispersed. (4) To provide a toner that has a small environmental dependency and a uniform charge amount. (5) To provide a toner having a good fixing property. (6) To provide a toner having a good cleaning property.

[0006]

To achieve the above object, the toner of the present invention has the following structural features. (1) Particles obtained by polymerizing a composition comprising a polymerizable monomer, a colorant, and an optional charge control agent, having a volume average particle diameter of 3.0 to 10.0 μm and a dispersity of 1 1 ~
It is characterized in that the degree of irregularity is 1.5 and the degree of indefiniteness is 1.3 to 3.0. (2) The volume average particle diameter of the particles a obtained by the polymerization reaction is 0.5 to 3.
The particle size is 0 μm, the dispersity is 1.1 to 1.8, and the particles b obtained by combining the particles a satisfy the relationship of the following expression 2.

[0007]

[Equation 2]

(3) A toner obtained by polymerizing a mixture of a composition containing core particles obtained from at least a polymerizable monomer, a colorant, and a release agent, and subjecting the mixture to a polymerization reaction.
The release agent has a volume average particle size of 0.5 to 3.0 in advance.
It is characterized in that it is added as a dispersion having a size of μm. (4) A toner obtained by polymerizing a mixture of a composition containing at least core particles obtained from a polymerizable monomer and a colorant, and subjecting the colorant to a primary particle size of 2 It is characterized in that it is added as a dispersion of 10 times. (5) The toner according to (2) above, which further comprises a release agent in the mixed liquid, and the release agent is a dispersion liquid having a volume average particle diameter of 0.5 to 3.0 μm in advance, and a colorant. Is added to the composition containing at least the core particles obtained by the polymerizable monomer as a dispersion liquid having a primary particle diameter of 2 to 10 times. (6) The composition containing the core particles obtained by at least the polymerizable monomer and the colorant are mixed in a solvent, and the pH of the mixed solution before the polymerization reaction is 2.0 to 6.5. Characterize.

(7) When the particles a in (2) above are obtained, the mixture further contains a release agent, and the pH of the mixture of the colorant dispersion and the release agent dispersion is 2.0 when mixed. It is characterized in that it is adjusted to ˜6.5 and a polymerization reaction is carried out. (8) The toner according to the above (2), wherein the composition containing at least core particles obtained from a polymerizable monomer and a colorant are mixed, and the solid content concentration is 5.0 to 30.0 wt. %, And particles a are polymerized in the range of 25 to 50 ° C., and particles b are polymerized in the range of 50 to 90 ° C. (9) The toner according to the above (5), wherein the mixed solution before the polymerization reaction has a pH of 2.0 to 6.5 and a solid content concentration of 5.0.
% To 30.0% by weight, particles a are polymerized in the range of 25 to 50 ° C., and particles b are polymerized in the range of 50 to 90 ° C.

The present invention will be specifically described below for each claim. (1) Toner according to claim 1 This toner is particles obtained by polymerizing a composition comprising a polymerizable monomer, a colorant, a release agent if necessary, and a charge control agent which can be optionally selected. And the volume average particle size is 3.
The toner has a dispersity of 1.1 to 1.5 and an amorphous degree of 1.3 to 3.0. Here, the volume average particle size and the degree of dispersion are the laser diffraction particle size distribution measuring device "HELOS" (manufactured by SYMPATEC).
It is measured by. The degree of dispersion σ is σ =
It is defined by Dv / Dp (Dv: volume average particle diameter, Dp: number average particle diameter). In addition, the degree of indefiniteness is defined by the following mathematical expression 3, and the BET measurement value and the measurement particle size are Micromeritic, Flowsorb 2
It was measured by a 300II type (fluid-type specific surface area automatic measuring device; manufactured by Shimadzu Corporation).

[0011]

[Equation 3]

The volume average particle diameter of the toner is 3.0 to 10.0.
When it is in the range of μm, it is possible to reproduce a high quality image having excellent resolution, and the cleaning property becomes good. On the other hand, when the volume average particle diameter is less than 3.0 μm, cleaning failure is likely to occur. On the other hand, when the thickness exceeds 10.0 μm, high image quality cannot be obtained and the resolution is 5 lines / mm.
It becomes the following.

When the toner dispersity is in the range of 1.1 to 1.5, good image quality without fog and toner scattering can be reproduced. On the other hand, the degree of dispersion is 1.
When it is less than 1, production becomes difficult due to the temperature and concentration gradient of the apparatus, solvent, etc., and it is extremely difficult in practice to obtain a toner in good yield. On the other hand, when it exceeds 1.5, selective development occurs, causing fog and toner scattering.

Toner irregularity is 1.3 to 3.0 μm
When it is in the range, the toner cleaning property is improved, and the fluctuation of the particle size distribution is small, and the stable charging property is exhibited. On the other hand, if the degree of irregularity is less than 1.3 μm, cleaning failure is likely to occur. on the other hand,
If it exceeds 3.0 μm, the toner is likely to be crushed in the developing device, so that the particle size distribution fluctuates and the charging property changes.

(2) Toner according to claim 2 This toner is a mixture liquid in which a composition containing at least core particles obtained by a polymerizable monomer, a colorant, and if necessary, a release agent are mixed to obtain a polymerization reaction. Particle a obtained by
However, the volume average particle size is 0.5 to 3.0 μm, and the dispersity is 1.
The particle size is 1 to 1.8, and the particle b obtained by combining the particles a is a toner that satisfies the relationship of the above-mentioned mathematical expression 2. In particular,
In the above formula 2, [volume average particle diameter of particle b / (particle a
The volume average particle diameter x the degree of dispersion of particles a)] is preferably 3 to 15. Here, the volume average particle diameter and the dispersity are measured in the same manner as in the case of the toner of claim 1.

The volume average particle diameter of the particles a is 0.5 to 3.0 μ.
When it is in the range of m, the toner has a small environmental dependence of charging and a uniform particle size distribution (particle b) by the emulsion polymerization method.
Can be manufactured stably. On the other hand, when the volume average particle size is less than 0.5 μm, the amount of the surfactant increases when the emulsion polymerization method is applied, the subsequent reaction is hindered, and the toner (particle b) is Environmental dependence of charging becomes large. On the other hand, when it exceeds 3.0 μm, stable production becomes difficult by the emulsion polymerization method, and the particle size distribution of the toner (particle b) becomes wide.

When the dispersity of the particles a is in the range of 1.1 to 1.8, it is possible to stably produce a toner (particles b) having a uniform particle size distribution. On the other hand, when the dispersity is less than 1.1, the release agent contained in the toner (particles b) must also be uniformly distributed, which makes manufacturing difficult. Further, it is extremely difficult in practice to set the dispersity to less than 1.1. On the other hand, when it exceeds 1.8, the particle size distribution of the toner (particle b) becomes wide.

When the particle b satisfies the above expression 2, the desired degree of indefiniteness can be obtained despite the small particle size. On the other hand, when the value is below the lower limit of the above formula 2, that is, [particle b
When the value of (volume average particle size of / a volume average particle size of particles a x dispersity of particles a)] is less than 3, the degree of indefiniteness of the toner becomes large. On the other hand, when the value exceeds the upper limit of the above mathematical expression 2, that is, when the value of [volume average particle diameter of particles b / (volume average particle diameter of particles a × dispersion degree of particles a)] exceeds 20, indeterminate The degree of cleaning tends to decrease, and cleaning failure tends to occur.

(3) Toner according to claim 3 This toner is obtained by a polymerization reaction of a mixed liquid containing a composition containing at least core particles obtained from a polymerizable monomer, a colorant and a release agent. The toner has a volume average particle diameter of 0.5 to 3.0 μm in advance.
Is added as a dispersion liquid. The volume average particle diameter of the release agent is measured in the same manner as in the case of the toner of claim 1. Thus, by adding the release agent in advance as a dispersion liquid having a volume average particle diameter of 0.5 to 3.0 μm, the dispersed state of the release agent in the toner can be made sufficiently uniform, and the hot offset A toner having excellent fixability can be obtained. In the dispersion liquid of the release agent, when the volume average particle diameter of the release agent is less than 0.5 μm, the effect of improving the fixability is small and the offset property and the like cannot be improved. On the other hand, when it exceeds 3.0 μm,
Since the toner is weak against heat and pressure, the toner is deformed and the particle size is reduced in the developing device, and it becomes difficult to stably convey the toner by the developing sleeve.

(4) Toner according to claim 4 This toner is a mixture liquid in which a composition containing at least core particles obtained by a polymerizable monomer, a colorant and, if necessary, a release agent are mixed, and a polymerization reaction is carried out. A toner obtained by allowing the colorant to have a primary particle size of 2 to 10 in advance.
It was added as a dispersion having a double particle size. The primary particle size of the colorant is an average particle size calculated from the size and number of the colorant particles by an electron micrograph, and the particle size of the colorant in the dispersion is “DLS-700” manufactured by Otsuka Electronics Co., Ltd. Measured by By thus adding the colorant as a dispersion having a particle size of 2 to 10 times the primary particle size in advance, the dispersed state of the colorant in the toner can be made sufficiently uniform and the image density is high. A toner having a high degree of blackening capable of forming an image is obtained. In the dispersion of the colorant, when the particle size of the colorant is less than twice the primary particle size, a sufficient concentration can be obtained with a small amount of the colorant.
Further, the environmental dependence of the toner can be reduced. On the other hand, when it exceeds 10 times, the content of the colorant becomes large, the environmental dependence becomes large, and it becomes difficult to achieve both transparency and reflectivity in the case of a color toner.

(5) Toner according to claim 5 This toner is the same as the toner according to claim 2, further comprising a releasing agent in the mixed liquid, wherein the releasing agent has a volume average particle diameter of 0.5 to 3. A dispersion liquid having a particle size of 0 μm and a coloring agent having a particle size of 2 to 10 times the primary particle size, which is added to a composition containing at least core particles obtained from a polymerizable monomer. Is. With such a toner, it is possible to stably produce a toner having a small environmental dependence of charging and a uniform particle size distribution by an emulsion polymerization method, and obtain a toner having excellent fixability and blackening degree. .

(6) Toner of claim 6 This toner is prepared by mixing at least a composition containing core particles obtained from a polymerizable monomer, a colorant and, if necessary, a releasing agent in a solvent and polymerizing. The pH of the mixed liquid before the reaction was set to 2.0 to 6.5. By thus regulating the pH of the mixed solution before the polymerization reaction to be in the range of 2.0 to 6.5, the respective materials in the mixed solution can be sufficiently uniformly aggregated, and the characteristics can be made uniform. Toner is obtained. On the other hand, when the pH of the liquid mixture is less than 2.0, the same material in the liquid mixture is likely to aggregate, and the toner composition becomes non-uniform. On the other hand, when the pH exceeds 6.5, the same material in the mixed liquid is likely to aggregate, resulting in non-uniform dispersion.

(7) Toner according to claim 7 This toner further comprises a release agent in the mixed liquid when the particles a according to claim 2 are obtained, and the dispersion liquid of the colorant and the dispersion liquid of the release agent. The pH was adjusted to 2.0 to 6.5 during the mixing, and the polymerization reaction was performed. Thus, when the dispersion of the colorant and the dispersion of the release agent are mixed, the pH is adjusted to 2.0 to 6.5 and the polymerization reaction is performed to obtain the particle a. The dispersed state of the agent can be made more uniform.

(8) Toner according to claim 8 This toner is the same as the toner according to claim 2, except that a composition containing at least core particles obtained from a polymerizable monomer, a colorant and, if necessary, a release agent are mixed. The solid content concentration of the mixed liquid is 5.0 to 30.0% by weight, and the particle a is 25 to 5%.
Polymerization is carried out in the range of 0 ° C., and particles b are polymerized in the range of 50 to 90 ° C. With such a configuration, the toner can be manufactured in a short time, and the toner having a uniform particle size distribution and a uniform composition can be obtained. On the other hand, when the solid content concentration of the mixed solution is less than 5.0% by weight,
Manufacturing takes time, resulting in an increase in manufacturing cost. on the other hand,
When it exceeds 30.0% by weight, the aggregate becomes large,
Wider particle size distribution. Moreover, the polymerization temperature of the particles a is 25 ° C.
When it is less than the above range, the reaction is slow and the production cost is increased.
On the other hand, when it exceeds 50 ° C., the particle composition of the aggregate becomes non-uniform. Further, when the polymerization temperature of the particles b is less than 50 ° C., the aggregating rate is low and the manufacturing cost is increased. On the other hand, when it exceeds 90 ° C., the particle composition of the aggregate becomes non-uniform.

(9) Toner according to claim 9 This toner is the same as the toner according to claim 5, except that the mixed solution before polymerization reaction has a pH of 2.0 to 6.5 and a solid content concentration of 5.0 to 30. 0% by weight, and the particles a at 25 to 50 ° C.
And the particles b are polymerized in the range of 50 to 90 ° C. With such a configuration, the toner can be manufactured in a short time, and the toner having a uniform particle size distribution and a uniform composition can be obtained.

(10) Common Items Next, constituent elements common to each of the toners according to claims 1 to 9 will be described. The polymerizable monomer may be any one that can synthesize a thermoplastic resin for toner, but a monomer used for obtaining a vinyl polymer is preferable. As the polymerizable monomer for obtaining the vinyl polymer, for example, those described in JP-A-56-106250 can be used. Specifically, styrene, o
-Methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl styrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenyl styrene,
Examples thereof include styrene-based monomers such as p-chlorostyrene and 3,4-dichlorostyrene.

Other vinyl monomers include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl halides such as vinyl fluoride and acetic acid. Vinyl, vinyl propionate, vinyl benzoate, vinyl butyrate, and other vinyl esters, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate
Octyl, dodecyl acrylate, lauryl acrylate,
2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloromethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Α-methylene aliphatic monocarboxylic acids such as, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like. Ester, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether Such as vinyl ethers, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and other vinyl ketones, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole,
Examples include N-vinyl compounds such as N-vinylpyrrolidene and vinylnaphthalenes.

When carrying out the polymerization reaction or the like on the acidic side, a monomer having an acidic polar group can be used at the same time as the vinyl monomer. As the monomer having an acidic polar group,
Acrylic acid, methacrylic acid, fumaric acid, maleic acid,
Itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid monooctyl ester, and carboxyl groups (--COO, etc.) of these metal salts such as Na and Zn.
[Alpha], [beta] -ethylenically unsaturated compound having H), sulfonated styrene, its Na salt, allyl sulfosuccinic acid,
Examples include octyl allyl sulfosuccinate and α, β-ethylenically unsaturated compounds having a sulfone group (—SO ₃ H) such as Na salt thereof. Further, anionic surfactants, nonionic surfactants, etc., which will be described later, can be used at the same time as the vinyl monomers.

When carrying out a polymerization reaction or the like on the basic side,
A monomer having a basic polar group can be used at the same time as the vinyl-based monomer. As the monomer having a basic polar group, a (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group and having 1 to 12 carbon atoms, preferably 2 to 8, and particularly preferably 2, (Meth) acrylic amide or (meth) acrylic amide optionally mono- or di-substituted with an alkyl group having 1 to 18 carbon atoms on N, vinyl substituted with a heterocyclic group having N as a ring member Compound, N, N-
Examples thereof include diallyl-alkylamine or a quaternary ammonium salt thereof. Among them, amine groups or 4
(Meth) of aliphatic alcohols containing quaternary ammonium groups
Acrylic acid esters are preferred. Further, a cationic surfactant, a nonionic surfactant, etc., which will be described later, can be used together with the vinyl monomer.

A cross-linking agent may be used in combination with the polymerizable monomer. Such cross-linking agents include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and their derivatives, ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl. Diethylenic carboxylic acid esters such as methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate,
Examples thereof include divinyl compounds such as N, N-divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone, and compounds having 3 or more vinyl groups.
These may be used alone or as a mixture. Further, as other crosslinking agents, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-
Propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,4
-Dihydric alcohols such as bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropyleneized bisphenol A, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itacone Acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid,
Cyclohexanedicarboxylic acid, succinic acid, adipic acid,
Dibasic acids such as sebacic acid, malonic acid, anhydrides of these acids or lower alcohol esters thereof and derivatives thereof, trihydric or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol, and trimellitic acid, pyromellitic acid Examples thereof include trivalent or higher carboxylic acids such as meritic acid.

As the releasing agent, for example, JP-A-56-11 is used.
The one described in Japanese Patent No. 0946 can be used,
Specific examples thereof include polyolefin wax, paraffin wax, oxidized paraffin wax, fatty acid ester wax, partially saponified fatty acid ester wax, 0001 mid wax, microcrystalline wax, and other waxes. Of these, polyolefin wax is preferable. Especially polypropylene wax,
Polyethylene wax is preferred. Further, polypropylene wax modified with a carboxylic acid such as maleic acid is preferable. Moreover, you may use together several types of polyolefin waxes. Commercially available polyolefin waxes include Viscole 330P, Viscole 550P, Viscole 660P (above, Sanyo Kasei Kogyo Polypropylene wax), High Wax 320P, High Wax 3
10P, high wax 410P, high wax 405
P, high wax 400P, high wax 200P (above, Mitsui Petrochemical Co., polyethylene wax), sun wax 131P, sun wax 151P, sun wax 161P, sun wax 165P, sun wax 17
1P (above, polyethylene wax manufactured by Sanyo Kasei Co., Ltd.), polywax 400, polywax 500, polywax OH465, polywax 1040 (all manufactured by Toyo Petrolite, polyethylene wax) and the like.

As the colorant, various organic pigments (azo pigments, polycyclic pigments, acidic or basic dyes), inorganic pigments (oxides, hydroxides, sulfides, selenides, ferrocyanides, chromic acids) Examples thereof include salts, sulfates, carbonates, silicates, phosphates, metal powders) and carbon. Specifically, carbon black, nigrosine dye, aniline blue, chalco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, these And mixtures thereof. Among these, carbon black is preferable as the black colorant, disazo pigment is preferable as the yellow colorant, quinacridone pigment is preferable as the magenta colorant, and copper phthalocyanine pigment is preferable as the cyan colorant.

Examples of charge control agents that can be arbitrarily selected include metal complex dyes, nigrosine dyes and ammonium compounds.

When obtaining the toner of the present invention,
If necessary, anionic, cationic, amphoteric, or nonionic surfactants may be used. For example, it is preferable to use an anionic surfactant when obtaining a negatively chargeable toner, and to use a cationic surfactant when obtaining a positively chargeable toner. Further, in order to further improve the dispersion stability, it is preferable to use a nonionic surfactant together. Examples of the anionic surfactant include fatty acid salts such as sodium oleate and castor oil potassium, alkyl sulfate salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and alkylnaphthalenesulfonates. , Dialkyl sulfosuccinate, alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate, and quaternary ammonium salts such as lauryltrimethylammonium chloride and stearyltrimethylammonium chloride.
As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin, fatty acid ester, oxyethylene- There are oxypropylene block polymers and the like. Examples of the zwitterionic surfactant include lauryl trimethyl ammonium chloride. The amount of the surfactant used is preferably 0.01 to 10% by weight, and particularly 0.5
-5% by weight is preferred. If the amount of the surfactant used is too small, stable emulsion polymerization may be difficult, and if the amount of the surfactant is excessive, the moisture resistance of the toner may be deteriorated.

When obtaining the toner of the present invention,
A water-soluble polymerization initiator may be used if necessary. Examples of such water-soluble polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, 4,4′-
Azobis cyanovaleric acid, 2,2'-azobis (2-amidinopropane) dihydrochloric acid, t-butyl hydroperoxide, cumene hydroperoxide and the like can be mentioned. These water-soluble polymerization initiators may be used in combination with a reducing agent. As the reducing agent, generally known ones such as sodium metabisulfite and ferrous chloride can be used. The reducing agent does not necessarily have to be used, but when it is used, it is preferably used in an equivalent amount or less with respect to the water-soluble polymerization initiator. The amount of the polymerization initiator used is preferably 0.01 to 10% by weight, and particularly preferably 0.1 to 5% by weight, based on the polymerizable monomer. When the amount of the polymerization initiator is too small, the polymerizable monomer is not completely polymerized and remains in the toner, possibly deteriorating the characteristics of the toner.

In the toner of the present invention, a fluidizing agent may be externally added and mixed if necessary. Examples of the fluidizing agent include inorganic oxides, inorganic nitrides, carbides, and organic fine particles. You may use these together suitably.

(11) Manufacturing Example of Toner Hereinafter, a specific manufacturing example of the toner will be described. Styrene-based, acrylic-based polymerizable monomers, polymerization initiator,
An emulsion is formed in an aqueous medium in which a crosslinking agent, a surfactant and the like are added as necessary, and the emulsion is heated at a temperature of 50 to 100.
The core particles are produced by maintaining the temperature at 0 ° C. and performing a polymerization reaction for 0.5 to 5 hours. Instead of polymerizing the core particles by carrying out the polymerization reaction as described above, polymerized fine particles of styrene type, acrylic type, epoxy type or the like may be used. On the other hand, the colorant is dispersed in an aqueous medium containing a surfactant.
In this dispersion, the particle size of the dispersed colorant is adjusted to be 2 to 10 times the primary particle size. Further, a release agent is dispersed in an aqueous medium to which a surfactant is added, and the temperature and pressure of this dispersion are increased to obtain a uniform dispersion state,
And the volume average particle diameter of the dispersed release agent is 0.5 to 3.0 μ.
Adjust to be m.

The core particles, the colorant dispersion, and the release agent dispersion obtained as described above are mixed, and while the pH is adjusted, the mixture is uniformly dispersed by a stirrer and agglomerated. To produce particles a. In this agglomeration,
The volume average particle size of the particles a is set to 0.5 to 3.0 μm. The temperature and pH of the dispersion are adjusted so that the dispersity of the particles a is 1.1 to 1.8, and the reaction is stopped. The dispersion liquid containing the particles a is further heated to a high temperature of 50 to 90 ° C. to promote coagulation, and the volume average particle diameter is 3.0 to 1
A toner composed of particles b having a particle size of 0.0 μm, a dispersity of 1.1 to 1.5 and an irregularity of 1.3 to 3.0 is obtained. Also,
The toner may be formed by externally adding and mixing a fluidizing agent to the toner.

Examples of the carrier used in combination with the toner of the present invention include carriers in which the surface of iron powder, ferrite powder or the like is coated with a resin. As the resin for coating, styrene-acrylic resin, fluorine resin,
Silicone resins and the like can be mentioned. Further, the form of the carrier may be either spherical or amorphous.

[0040]

[Example 1]

Styrene monomer 85 parts Butyl acrylate 15 parts Acrylic acid 5 parts Water and above materials 500 parts Nonionic surfactant (polyoxyethylene alkyl ether) 2 parts Cationic surfactant (dimethyl ammonium chloride) 2 parts Polymerization initiator (Potassium persulfate) Pour into an aqueous solution mixed with 2 parts, K. The mixture was stirred while maintaining the temperature at 80 ° C. in a container equipped with a formula homomixer. In a device equivalent to the above, 100 parts of water, 2 parts of polypropylene, and 2 parts of anionic surfactant (alkylbenzene) were put, the container was pressurized and kept at 120 ° C. K. The particle size of polypropylene dispersed particles was adjusted to 1.0 μm by stirring at 10,000 rpm with a homomixer. Further, in an apparatus equivalent to the above, add 100 parts of water and carbon black 1
0 parts and anionic surfactant (alkylbenzene) 2
Part, and T. K. Type homomixer 10,000 rp
The particle diameter of the dispersed particles of carbon black was made 3 times the primary particle diameter by stirring at m.

The above-mentioned three mixed solutions were combined into one and kept at 40 ° C. for 4 hours to obtain particles a. At this time, the pH was adjusted to 5.0 with hydrochloric acid. The particle diameter of the particles a is measured by a laser diffraction particle size distribution measuring device “HELOS” (SYMP
The volume average particle diameter was 2.2 μm and the dispersity was 1.6. Furthermore, the temperature was raised to 60 ° C. and held for 6 hours to form a complex,
Ammonia water was added to adjust the pH to 5.0 to control the complex reaction to obtain particles b having a volume average particle diameter of 5.1 μm, a dispersity of 1.4, and an amorphous degree of 2.0. It was Also,
The value of [volume average particle diameter of particles b / (volume average particle diameter of particles a × dispersion degree of particles a)] was 3. The main conditions for the above particles a and particles b are collectively shown in Table 1 below. The particles b were washed with water and dried to obtain a toner. To this toner, silica was added in an amount of 2% by weight and titanium oxide was added in an amount of 1% by weight, and 5 parts of this externally added toner and ferrite particles (carrier) 95 surface-coated with a methyl methacrylate / styrene copolymer were mixed. To prepare a developer.

Using this developer, an electrophotographic copying machine "UB" equipped with a heat roller fixing device and a cleaning blade is used.
ix3032 "(manufactured by Konica Corp.) was used to perform a live-copy test to form a copy image, and the following items were evaluated. The results are shown in Table 2 below. (1) A copy image of a resolution fine line chart was formed and judged by the number of distinguishable fine lines per 1 mm. (2) Fog “Sakura densitometer” that continuously forms copy images under normal temperature and normal humidity environment (temperature 20 ° C, relative humidity 60%).
The reflection density of the white background portion was measured by (manufactured by Konica Corp.), and the fog was judged by the number of copies when the reflection density exceeded 0.02. (3) Hot Offset Occurrence Temperature A copy image was formed while changing the set temperature of the fixing roller stepwise, and the set temperature of the fixing roller at the time when toner stain due to hot offset occurred was measured and evaluated.

(4) Toner Blackness A single layer of toner was attached to a white label, and the reflection density of this toner layer was measured with a "Sakura densitometer" (manufactured by Konica Corp.) When the concentration was 1.3 or more, it was evaluated as ◯, and when it was less than 1.3, it was evaluated as x. (5) Cleaning Property The surface of the photoconductor was visually observed and evaluated by the number of copies when the cleaning failure occurred. (6) Change in particle size distribution The number% of toner particles having a volume average particle size of 1/3 or less was evaluated. The volume average particle diameter is measured by a laser diffraction type particle size distribution measuring device “HELOS” (manufactured by SYMPATEC). The measurement was carried out at the start of the actual shooting test and at the time of fog occurrence or when 50,000 copies were made, and changes over time were examined. If the number% of toner particles having a volume average particle diameter of ⅓ or less is 10% or more, the charging property of the toner is hindered.

Example 2 In the same manner as in Example 1, particles a having a volume average particle size of 2.2 μm and a dispersity of 1.6 were obtained. A styrene monomer 85 was added to the dispersion liquid containing the particles a.
Parts, 15 parts of butyl acrylate, 5 parts of acrylic acid,
A mixture with 2 parts of a polymerization initiator (potassium persulfate) was added dropwise, and the mixture was polymerized at a temperature of 60 ° C. for 6 hours. The volume average particle diameter was 3.0 μm, the dispersity was 1.5, and the degree of indefiniteness was 1.
Particles 5 of 5 were obtained. The particles b were washed with water and dried to obtain a toner. In the same manner as in Example 1, this toner was mixed with an external additive and further with a carrier to prepare a developer. Using this developer, an actual copying test was conducted in the same manner as in Example 1, and the results shown in Table 2 below were obtained.

[Examples 3 to 6] In the same manner as in Example 1 except that the reaction conditions were changed, particles b having a volume average particle size, a dispersity and an amorphous degree shown in Table 1 below were obtained. .
A developer was prepared in the same manner as in Example 1 using the particles b, and a live-copy test was conducted. The results shown in Table 2 below were obtained.

[Comparative Examples 1 to 6] In the same manner as in Example 1, except that the reaction conditions were changed, particles b having the volume average particle size, dispersity, and indefiniteness shown in Table 1 below were obtained. .
A developer was prepared in the same manner as in Example 1 using the particles b, and a live-copy test was conducted. The results shown in Table 2 below were obtained.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

As described in detail above, according to the present invention, the following effects can be obtained. (1) A small-diameter irregular toner capable of forming a high-resolution image is obtained. (2) A toner having a uniform particle size distribution can be obtained. (3) A toner in which the colorant and the release agent are uniformly dispersed can be obtained. (4) A toner having a small environmental dependency and a uniform charge amount can be obtained. (5) A toner having good fixability can be obtained. (6) Toner with good cleaning properties can be obtained.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yuuo Endo             2970 Ishikawa-cho, Hachioji-shi, Tokyo Konica stock             In the company

Claims (9)

[Claims] 1. Particles obtained by polymerizing a composition comprising a polymerizable monomer, a colorant, and an optional charge control agent, having a volume average particle diameter of 3.0 to 10.0 μm and a dispersity degree. Is 1.1 to 1.5 and the degree of indefiniteness is 1.3 to 3.0. 2. A mixed liquid in which a composition containing core particles obtained by at least a polymerizable monomer and a colorant are mixed,
The particles a obtained by the polymerization reaction have a volume average particle size of 0.
A toner having a particle size of 5 to 3.0 μm and a dispersity of 1.1 to 1.8, and particles b obtained by combining the particles a satisfy the relationship of the following formula 1. [Equation 1] 3. A toner obtained by polymerization reaction of a composition containing at least core particles obtained from a polymerizable monomer, a colorant, and a release agent, wherein the release agent is The volume average particle size is 0.5 to 3.0 in advance.
A toner which is added as a dispersion having a size of μm. 4. A mixed solution in which a composition containing at least core particles obtained from a polymerizable monomer and a colorant are mixed,
A toner obtained by a polymerization reaction, wherein the colorant is added in advance as a dispersion having a primary particle diameter of 2 to 10 times. 5. The toner according to claim 2, further comprising a release agent in the mixed liquid, the release agent being a dispersion liquid having a volume average particle diameter of 0.5 to 3.0 μm in advance. A toner containing a colorant as a dispersion having a particle size of 2 to 10 times the primary particle size, which is added to a composition containing at least core particles obtained from a polymerizable monomer. 6. The pH of the mixed solution before the polymerization reaction is carried out by mixing in a solvent a composition containing core particles obtained by at least a polymerizable monomer and a colorant. Toner characterized by that. 7. When the particles a according to claim 2 are obtained, a release agent is further included in the mixed liquid, and the pH is 2.0 when the dispersion liquid of the colorant and the dispersion liquid of the release agent are mixed. The toner is characterized in that it is adjusted to ˜6.5 and is polymerized. 8. The toner according to claim 2, wherein a mixture containing at least a composition containing core particles obtained from a polymerizable monomer and a colorant has a solid content concentration of 5.0 to.
The toner is 30.0% by weight, and the particles a are polymerized in the range of 25 to 50 ° C., and the particles b are polymerized in the range of 50 to 90 ° C. 9. The toner according to claim 5, wherein the mixture liquid before the polymerization reaction has a pH of 2.0 to 6.5 and a solid content concentration of 5.0 to 30.0 wt%. Particle a 25 ~
A toner characterized in that it is polymerized in a range of 50 ° C. and particles b are polymerized in a range of 50 to 90 ° C.