JPH07258306A - Manufacture of resin particle and developing agent - Google Patents

Abstract

PURPOSE:To manufacture resin particles having excellent water resistance and moisture resistance through soap-free emulsion polymerization by polymerizing an aq. dispersion contg. a polymerizable monomer, a resin emulsion, and a particular oligomer. CONSTITUTION:An aq. dispersion is polymerized which contains a polymerizable monomer (e.g. styrene), a resin emulsion prepd. pref. by soap-free polymn. (e.g. a resin emulsion prepd. by polymerizing styrene and n-butyl acrylate in the presence of ammonium persulfate), and an oligomer having a hydrophobic portion which is the same as a hydrophobic portion comprising a monomer skeleton in a repeating structure of the resin (e.g. an anionic oligomer which is produced together with the resin emulsion in the manufacture of the resin emulsion: a compound of the formula wherein n is 1 to 10 and R1 represents a C1 to C6 alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing resin particles by soap-free polymerization. Further, the present invention relates to a method for producing a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like by using soap-free polymerization.

[0002]

Conventionally, as a method for producing resin particles, an emulsion polymerization method in which a surfactant and a water-soluble polymer emulsifier are used alone or in combination, a soap-free polymerization method using a reactive emulsifier which is a water-soluble polymerization initiator, There is a soap-free polymerization method using a water-soluble polymerized monomer and a reactive emulsifier which is a water-soluble polymerization initiator. In these manufacturing methods, in recent years, it has been desired to clean industrial wastewater as a part of environmental problems, and there are many composite resin particles for which moisture resistance and water resistance are desired, such as polymerized toner and film latex.

Hitherto, there have been the following methods for making industrial wastewater pollution-free and improving the moisture resistance and water resistance of products. For example, in a production method using a highly hydrophilic surfactant and a water-soluble polymer emulsifier, it is difficult to remove them by washing, and therefore a water-soluble organic solvent is used (JP-A-2-
245768), acid treatment, alkali treatment (JP-A-1-86)
160 etc.), high temperature treatment (JP-A-4-81430 etc.), coupling treatment (JP-A-3-89361 etc.), saponification treatment (JP-A-1-257859 etc.) and the like have been required. Further, as a method for cleaning industrial wastewater and improving moisture resistance, use of a water-soluble polymerizable monomer for reducing the amount of a surfactant (Japanese Patent Laid-Open No. 1-298367).
Etc.) and the use of self-emulsifying polymer emulsifiers in place of water-soluble polymer emulsifiers (JP-A-64-59239, etc.). It was difficult to synthesize particles.

Further, as composite resin particles by a soap-free emulsion polymerization method, for example, in JP-A-63-205665 and JP-A-63-281172 regarding the method of producing a polymerized toner, there are surfactants for dispersing components to be composited. The advantages of soap-free products tend to be impaired due to the fact that they are used.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and provides a method for producing resin particles having excellent water resistance and moisture resistance, and further, a method for producing industrial wastewater by soap-free polymerization of resin particles. For the purpose of pollution.

Another object of the present invention is to provide a method for producing a polymerized developer excellent in water resistance and moisture resistance and a method for producing a developer by soap-free polymerization excellent in water resistance and moisture resistance.

[0007]

The first aspect of the present invention is as follows.
Polymerizing an aqueous dispersion containing a polymerizable monomer, a resin emulsion obtained by soap-free emulsion polymerization, and an oligomer having the same hydrophobic part as the hydrophobic part consisting of the monomer skeleton in the repeating structure of the resin Provided is a method for producing resin particles, which comprises steps.

A second aspect of the present invention is a polymerizable monomer,
Characterized by polymerizing an aqueous emulsion containing a resin emulsion obtained by soap-free emulsion polymerization, an oligomer having a hydrophobic part identical to the hydrophobic part consisting of a monomer skeleton in the repeating structure of the resin, and a colorant. Provided is a method for producing a developer.

A third aspect of the present invention is a polymerizable monomer,
Aqueous dispersion containing a resin emulsion obtained by soap-free emulsion polymerization, an oligomer having a hydrophobic part which is the same as the hydrophobic part consisting of a monomer skeleton in the repeating structure of the resin, a colorant, and a self-emulsifying emulsion wax Provided is a method for producing a developer, which comprises a step of polymerizing a liquid at pH 3 to 6.

A fourth aspect of the present invention is a polymerizable monomer,
Provided is a method for producing resin particles, which comprises a step of polymerizing an aqueous dispersion containing a reactive emulsifier and an oligomer having a polar group having a polarity opposite to that of a polar group of a decomposed fragment of the reactive emulsifier.

A fifth aspect of the present invention is a polymerizable monomer,
An aqueous dispersion containing a reactive emulsifier, an oligomer having a polar group having a polarity opposite to the polar group of the decomposed segment of the reactive emulsifier, a colorant, and a self-emulsifying emulsion wax is added to pH.
Provided is a method for producing a developer, which comprises the step of polymerizing in 3 to 6.

[0012]

In the first, second and third aspects of the present invention,
One of its important characteristics lies in the oligomer used.
A schematic diagram showing the structure of the oligomer used in the present invention is shown in FIG. As shown in FIG. 1, it has a hydrophobic group 303 having a repeating structure of a polar group as a terminal group 302 and a resin monomer skeleton. Therefore, it has a low affinity with water. The compatibility with the polymerized monomer can be enhanced by adsorbing the oligomer to the resin emulsion or further adsorbing the specific oligomer to the composite component such as the filler. Although the composite particles are produced by carrying out the polymerization in such a state, even if the oligomer remains, the moisture resistance of the particles is not lowered.

By using the oligomer in which the hydrophobic part is in the hydrophobic part consisting of the repeating structure of the monomer skeleton of the resin, the compatibility with the resin is improved and the monomer is swelled easily. The miscibility of the resin and other components is improved. Further, even if it remains in the composite particles after the polymerization, it is the same as the resin component of the particles and does not adversely affect the properties.

In the second aspect of the present invention, a developer is obtained by adding a coloring material to the first aspect. In the third aspect of the present invention, a developer is obtained by dispersing and polymerizing the oligomer, resin emulsion, colorant and wax used in the first aspect. The reason why the wax is a self-emulsifying emulsion is that it contains no surfactant or emulsifier. Further, a pH in the range of pH 3 to 6 is preferable because the self-emulsification type emulsion wax has an isoelectric point near 2.5, so that aggregation occurs at a pH lower than that vicinity and the isoelectric point of the cationic oligomer. Since the point exists near 7.0, aggregation occurs again at a pH higher than that point, so that the polymerization is inhibited.

In the fourth aspect of the present invention, one of its important features is an oligomer having a polar group having a polarity opposite to that of the decomposed fragment of the reactive emulsifier. The reason why this configuration is effective for making the drainage soap free will be described with reference to FIG. FIG. 2 is a model diagram showing a state in which a decomposed piece of the reactive emulsifier used in the present invention and an oligomer of opposite polarity are integrated and deposited on the surface of polymer particles. Here, the term “decomposed section” refers to a polar group when the reactive emulsifier is decomposed at high temperature. As shown in FIG. 2, the reactive emulsifier generates radicals in the decomposed section 403 in the aqueous phase 402, and the swollen 408 monomer is polymerized and grown from the oil phase 401 to the decomposed section 4
03 and the opposite polarity oligomer 404 are integrated to form hydrophobic fine particles 405 and 406 which are deposited on the surface of the polymer particles 407. Thus, the third aspect of the present invention
In the embodiment, the fine particles 405, 406 made of an oil-soluble substance are obtained by integrating the reactive emulsifier and the oligomer of opposite polarity.
Are deposited and the surface of the polymer particles is subjected to a hydrophobic treatment, and exhibits extremely excellent moisture resistance and water resistance.

In a fifth aspect of the present invention, a fragment of the reactive emulsifier used in the fourth aspect and an oligomer having a polar group having a polarity opposite to the polar group of the fragment, a colorant and a self-emulsifying agent are used. A developer is obtained by dispersing and polymerizing the type emulsion wax. Similar to the third aspect of the present invention, the reason why the wax is a self-emulsifying emulsion is that it does not contain extra surfactant or emulsifier. The reason for adjusting the pH is that the self-emulsification type emulsion wax has an isoelectric point of around 2.5, so that aggregation occurs at a pH lower than that vicinity, and either the reactive emulsifier segment or the oligomer is cationic. Since the isoelectric point is around 7.0, a suitable pH is 3 because agglomeration will occur again at a pH higher than that.
~ 6.

[0017]

EXAMPLES A color image forming apparatus applicable to the developer according to the present invention will be described below. FIG. 6 shows a color image forming apparatus in which the developer according to the present invention can be used. As shown in FIG. 6, in the present apparatus, the photoconductor 201, the charging device 202, the laser exposure device 203, the developing device 200, the transfer device 209, the blade cleaning device 204, and the discharging lamp 205 are black, yellow, magenta, and cyan. Four sets of colors are arranged. A transfer material 213 such as paper or OHP sheet is conveyed on the transfer belt 208 from the direction of the arrow, and a transfer voltage is applied by the transfer device 209 from the lower side of the transfer belt 208 at a portion in contact with the photoconductor 202. The toner developed on the photoconductor 202 in the developing process is transferred to the transfer material 213. This is sequentially performed for each color, and the toner image is superimposed on the transfer material 213.

As the transfer device 109, a device for applying a bias voltage to an elastic roller is used. The toner image superimposed on the transfer material 213 is fixed to the fixing device 2.
The toner is heated by passing between the heating roller 211 and the pressure roller 212 in 10 to be fixed on the image support. In this way, a full-color image is obtained.

As a developing method, a two-component developer consisting of a magnetic carrier and a non-magnetic toner, a developer consisting of a magnetic carrier and magnetic and non-magnetic toner, a magnetic one-component developer consisting only of a magnetic toner, and a non-magnetic toner only. There is a developing system using various developers such as a one-component non-magnetic developer.
Among them, the mechanical stress on the toner is caused by the collision and friction between the toners or the carrier in the case of the developer using magnetic particles, or the friction with the doctor blade that regulates the layer thickness of the developer. Furthermore, there is a cause of collision and friction with the stirring means in the developing device.
The non-magnetic one-component developing method will be described in more detail later with reference to other drawings.

On the other hand, the fixing device 7 is composed of two elastic rollers, or one of them is a metal roller, and the heat source may be on both rollers or on one side only. Since the offset phenomenon occurs when the toner melts at a high temperature, a solid or liquid release agent is applied to the roller surface. In particular, in the case of color toner, which requires transparency at the time of fixing, a release agent such as silicone oil is constantly replenished.

In the cleaning device 8, the cleaning blade 1 which is an elastic member fixed to the support member 11 is used.
The residual toner on the photoconductor 1 rotating in the direction of the arrow (A) is scraped in the cleaning device 8 by the cleaning blade 10.
This method is the most common and compact cleaning method called the blade cleaning method, but when cleaning is not sufficiently performed, a fur brush,
A method of scraping with a brush such as a magnetic brush may be used alone or in combination with a blade method.

The materials that can be used for the resin particles and the developer of the present invention will be described below. As the polymerizable monomer used in the present invention, vinyl aromatic monomer, acrylic monomer, vinyl ester monomer, vinyl ether monomer, diolefin monomer, monoolefin monomer. It is a quantity etc. Examples of the monovinyl aromatic monomer include monovinyl aromatic hydrocarbons such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene,
Examples thereof include o-, m-, p-chlorostyrene, p-ethylstyrene, and divinylbenzene, which may be used alone or in combination of two or more. Examples of acrylic monomers include methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
Cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-hydroxyacrylate, butyl δ-hydroxyacrylate, β-hydroxymethacrylic acid Ethyl, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc. Examples of vinyl ester-based monomers include vinyl formate,
Vinyl acetate, vinyl propionate, etc. Examples of vinyl ether-based monomers include vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl ether, vinyl cyclohexyl ether and the like. Examples of the diolefin-based monomer include butadiene, isoprene and chlorobrene. Monoolefin monomers include ethylene, propylene, isobutylene,
Butene-1, pentene-1, 4-methyl pentene-1 etc. are mentioned.

The oligomer used in the present invention has a hydrophobic part consisting of a repeating structure of the above-mentioned polymerizable monomer alone or a copolymer skeleton of two or more kinds, and a polar group of weak acid or weak base as an end group. It is a thing. As the terminal group, for example, anionic fatty acid salt type -COONH is used.
4 and the like, sulfate ester type —OSO3 NH4 and the like, phosphoric acid ester salt type —OSO3 (NH4) 2 and the like, and cationically amine salt type 1,2,3 secondary alkylamines, 1,2, Examples thereof include tertiary ethanolamines, polyethylene polyamines, and the like, and ethylene oxide adducts of alkylamines that exhibit weak cationicity by being polarized by weak hydration in water. In order to improve moisture resistance and water resistance, amines are neutralized with relatively weakly acidic lower fatty acids such as formic acid and acetic acid. As a concrete example of an oligomer, as one having a styrene derivative structure

[0024]

[Chemical 1]

CH2 = CR1COO (CH2) n-NR2R3, etc. having an alkaline acid derivative structure, etc., and further having a styrene acrylic acid copolymer derivative structure, etc.

[0026]

[Chemical 2] And so on. (N: integer of 1 to 10, R1, R
2, R3: an alkyl group having 1 to 6 carbon atoms) Further, other than the above, itacoi acid derivative, maleic acid derivative, fumaric acid derivative, allyl alcohol derivative, succinic acid derivative, urethane derivative, styrene maleic acid resin, its half ester, etc. However, the present invention is not limited to the above.

For the purpose of neutralizing moisture resistance and water resistance, it is desirable to select highly volatile substances such as ammonia ions or amine ions and weak acids such as acetic acid and formic acid for neutralization.

As for the molecular weight of the hydrophobic part, it does not form associated micelles like ordinary emulsifiers but becomes micelles by itself, so that it becomes soap-free and cleanliness of drainage is improved. Tens of thousands are suitable, and the amount used is 0.01 to 30% by weight of the solid content, preferably less than the effect of residual moisture resistance and water resistance compared to usual emulsifiers, surfactants and polymer electrolytes, Is 0.1 to 1
It is 5% by weight.

The term "oligomer" as used herein means a low molecular weight polymer having a molecular weight of 100 to 10 ⁴ among polymers. Further, the term “decomposed section” refers to a polar group when the reactive emulsifier is decomposed at high temperature.

In the first and third aspects of the present invention,
It is possible to produce composite particles by further adding a filler that composites with the resin to the aqueous dispersion. Examples of such fillers include, in addition to colorants, charge control agents, film forming aids, antifreezing agents, antiseptics, antifungal agents, rust preventives, crosslinking agents, aggregates, and the like.

The term "composite" as used herein means a state in which different components are contained in the resin fine particles. The polar group of the terminal group of the oligomer is preferably a weak acid or a weak base.

By using a weak acid or a weak base in the polar group, the hydration power of the oligomer is weakened and the hydrophobicity is increased, so that even if it remains in the composite particles after the polymerization, there is little adverse effect on the moisture resistance and water resistance. At this time, a weak acid or a weak salt can be used to neutralize the oligomer, and the counter ion 301 can be an acetate ion, a formate ion, an ammonium ion, an amine ion, or the like.

It is preferable that at least one oligomer having a cationic terminal group is contained as the oligomer. When at least one of the oligomers is cationic, heteroaggregation contributes to the composite of the resin and other components. Especially when an oligomer is used here, it is less likely to form associated micelles like ordinary emulsifiers, and the tendency to become micelles by itself is strong, so that soap-free drainage and cleaning are improved, and ordinary water-soluble polymers are used. As described above, since there are no plural hydrophilic groups, the residue does not impair the moisture resistance and water resistance.

As the polymerization initiator used in the present invention, an azo compound such as azobisisobutyronitrile as an oil-soluble initiator soluble in a monomer, cumene hydroperoxide,
Examples thereof include peroxides such as dicumyl peroxide, benzoyl peroxide and lauroyl peroxide. Further, as the reactive emulsifying agent and the reactive surfactant, ammonium persulfate whose decomposition section is anionic, persulfate such as sodium persulfate and potassium persulfate, and DEAM which is cationic
(N, N'-diethylaminoethyl methacrylate),
Examples include AIBN · 2HCl (isobutyramide hydrochloride).

Other examples include polyoxyethylene methacrylate, dimethylaminoethyl, and diethylaminoethyl methacrylate acetate. Again, by selecting a highly volatile counter ion such as ammonia ion or amine ion, moisture resistance,
Water resistance is further improved. The amount used is 0.01 to 10 with respect to the polymerizable monomer because the polymerizable monomer is completely polymerized.
% By weight, preferably 0.1 to 5% by weight.

The resin emulsion used in the present invention is produced by soap-free emulsion polymerization of the above-mentioned polymerizable monomers used in the present invention alone or in combination of two or more kinds with a reactive emulsifier. For example, polystyrene, styrene-acrylic copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, polyethylene, polypropylene, polyurethane, polyester resin, epoxy resin, silicone resin, polyamide , Paraffin and the like. The molecular weight of the resin emulsion is preferably 10,000 to 1,000,000 in terms of weight average molecular weight, and the size is preferably 10 times or more that of the filler compounded with the average particle diameter.

In the present invention, the resin emulsion is
It is preferably obtained by soap-free polymerization. When using a resin emulsion by soap-free emulsion polymerization, in order to improve the moisture resistance and water resistance of the resin that occupies the main part of the particles and to clean the drainage, in the first stage,
It is possible to prevent the mixing of extra components such as a highly hydrophilic surfactant and an emulsifier.

In the present invention, as mentioned above, as the composite filler which can be further added to the aqueous dispersion,
In addition to the colorant, for example, a charge control agent, a film-forming auxiliary agent, an antifreezing agent, an antiseptic agent, an antifungal agent, an anticorrosive agent, a crosslinking agent, an aggregate and the like can be mentioned.

As the pigment of the colorant, inorganic pigments (natural,
Chromates, ferrocyanines, oxides, chlorides, sulfates, silicates, metal powders, etc., organic pigments (natural dye lake, nitroso type, azo type, phthalocyanine type, condensed polycyclic type, basic dye lake) , Mordant dyes, vat dyes, etc.),
Examples of dyes include water-soluble dyes and oil-soluble dyes. Specific examples of the inorganic pigment include, for example, natural pigments such as ocher, yellow lead, zinc yellow, barium yellow, chrome orange, molybdenum red, chromate salts such as chrome green, ferrocyan compounds such as dark blue, titanium oxide, and the like. Titanium yellow, white titanium, red iron oxide, yellow iron oxide, zinc ferrite, zinc white, iron black, cobalt blue, chromium oxide, oxides such as spinel green, sulfides such as cadmium yellow, cadmium orange, cadmium red, barium sulfate, etc. Examples thereof include sulfates, calcium silicates, silicates such as ultramarine blue, metal powders such as bronze and aluminum, and carbon black. Specific examples of the organic pigment include, for example, natural lakes such as Madarak, nitroso pigments such as naphthol green and naphthol orange, benzine yellow G, hansa yellow G, hansa yellow 1
0G, Vulcan Orange, Rake Red R, Rake Red C, Rake Red D, Watching Red, Brilliant Angamine 6B, Pyrralozone Orange, Bordeaux 10G
Soluble azo such as (Bon Maroon), pyrarozone red,
Para Red, Toluidine Red, ITR Red Toluidine Red (Rake Red 4R), Toluidine Maroon,
Insoluble azo pigments such as Brilliant Fight Scarred and Lake Bordeaux 5B, azo pigments such as condensed azo pigments, phthalocyanine blue, phthalocyanine green, brominated phthalocyanine green, phthalocyanine pigments such as fast sky blue, anthraquinone pigments such as slene blue, perylene Perylene-based pigments such as maroon, perinone-based pigments such as perinone orange, quinacridone-based pigments such as quinacridone and dimethylquinacridone, dioxazine-based pigments such as dioxazine violet, isoindoline-based pigments, quinophthalone-based condensed polycyclic pigments, rhodamine 6B, lake, Basic dye lakes such as Rhodamine Lake B and Malachite Green, mordant dye pigments such as Alizarin Lake, vat dye pigments such as Induslen Blue, Indigo Blue and Antoanthrone Orange. Fluorescent pigment, azine pigment (diamond black), green gold and the like. Specific examples of water-soluble dyes include basic dyes such as rhodamine B, acid dyes, fluorescent dyes, and specific examples of oil-soluble dyes include monoazo dyes such as Fast Orange R, oil red, oil yellow, and anthraquinone. Examples thereof include anthraquinone dyes such as blue and anthraquinone violet, azine dyes such as nigrosine and indulin, and basic, acidic and metal complex compound dyes.

Further, as an inorganic filler, as an oxide,
Iron oxide (FeO3), alumina (Al2 O3), magnesium oxide (MgO), titanium oxide (TiO2), zinc oxide (ZnO), NiO, SnO, TiBaO3, Ce
In addition to metal oxides such as O2, SrTiO3, CrO, tin oxide, indium oxide, and cerium oxide, fatty acid metal salts such as zinc stearate, calcium stearate, lead stearate, and other inorganic substances such as basic bismuth acetate, PM
Examples thereof include MA, styrene-acrylic copolymer, vinylidene fluoride, and fluororesin such as ethylene tetrafluoride.
As silicic acid and silicate, SiO2 (silica etc.), calcium silicate, aluminum silicate (clay etc.), magnesium silicate (talc, mica, attapulgite etc.), etc. as carbonates CaCO3, NiCO3, BaCO3
, Zirconium, strontium carbonate, etc. as sulfates such as barite (BaSO4), gypsum (CaSO4)
) Such as Mg (OH) 2, Mn (O
H) 2, hydroxide of barium, and other chlorides such as lead (second), glass, metal, and fiber. These fillers may be those surface-hydrophobized with a coupling agent such as a silane coupling agent, a titanium coupling agent, a zircoaluminate coupling agent, or a silicone oil.

As the charge control agent, a negative charge control agent is an electron-donating substance such as a nigrosine dye or a quaternary ammonium salt, and a positive charge control agent is an electron such as a metal salt of a monoazo dye. Inhalable substances are mentioned.

The amount of the above fillers used depends on the purpose and components thereof, but in many cases it is 0.1 to 50 parts, preferably 0.1 to 10 parts, and when it is 50 parts or more, it affects the polymerization. It will be difficult depending on the size of the material contained.

The self-emulsifying emulsion wax used for preventing offset of the polymerized developer, which is an example of the composite resin particles according to the present invention, is a carboxyl group-modified polyolefin, such as ethylene, propylene, butene-1, pentene-. Examples thereof include polyethylene waxes and polypropylene waxes which have been modified to have a carboxyl group having an olefin unit such as 1 as a skeleton and at least a part of the carboxyl groups are neutralized with ammonia or humin. The amount used is usually 0 to 30% by weight, preferably 1
~ 30% by weight.

The solid content for the production of the resin particles of the present invention is in the usual range of 1 to 30% by weight, preferably 3%.
To 20% by weight, and the average particle size of the polymerized toner is 1 to 1
The thickness is 00 μm, preferably 2 to 20 μm. The polymerization temperature and time may be those known in the art. Generally, polymerization at a temperature of 40 to 100 ° C. for 1 to 50 hours is sufficient, but the reaction time required for the polymerization system of the present invention tends to be particularly short,
In addition, the generation rate of new particles is extremely low even when the amount of oligomer added is increased.

Hereinafter, the present invention will be described in more detail with reference to specific examples of production methods and comparative examples, but the present invention is not limited thereto. Unless stated otherwise, quantities are indicated by weight. First, the tests performed in Examples and Comparative Examples will be described below.

1) Miscibility test of resin and component: Zeta potential of resin, composite component, and oligomer dispersion is 20 mV.
Above is ○, and when it is small, ×. (Zeta potential is PENKE
Measured by Model 501 of Company M under the condition of PH 5.0. ) 2) Resin-component composite test: The composite ratio to the charged amount of the composite component was determined by image processing of a TEM cross-sectional photograph of the final particles, and 80% or more was ◯, otherwise x. (The cross-section photo is
H-600 type TE manufactured by Hitachi
Observe with M. ) 3) Moisture resistance, water resistance test: The final particles are kept at room temperature and normal humidity of 20 ° C.
0% (N / N) and high temperature / high humidity 30 ° C. 85% (H / H) were placed in an environment for 12 hours, and the moisture content was measured. X. (The moisture content is measured by the Karl Fischer method at a sample heating temperature of 200 ° C. and a required time of 15 minutes.) 4) Drying property test: The washed particles have a moisture content of 0.5% or less after drying at 45 ° C. for 12 hours. ○, large is ×.
(Measurement method of moisture content is the same as above.) 5) Fogging test (moisture resistance test of polymerized toner): The polymerized toner of the present invention is mixed with a ferrite carrier having an average particle diameter of about 60 μm in a weight ratio of 100: 4, and two-component development is performed. Device and heat roller heat fixing device with surface temperature of 128 ° C (nip width 7.5 m
m) and a blade cleaning device, and used as a developer for the printer shown in FIG. 6 having a process speed of 65 mm / sec. The resulting polymerized toner was dried at 45 ° C. for 50 hours, then at 20 ° C. 50% (N / N), the latent image on the photoreceptor of the 1000th sheet of image output was lightened (%) by taping with a commercially available mending tape. , Then 30 ℃ 85% (H /
In H), the brightness (%) of the taped latent image on the first photoconductor after 12 hours was compared, and when the difference was 5% or more, it was ×, and when it was small, ○ (the measurement of the lightness was (Measured with a color difference meter Minolta CR-10.) 6) Cleanliness test of wastewater: When 20% or more of the charged amount of oligomer is detected by quantitative analysis of wastewater, x, 1
△ is 0% or more, ○ is less than. (For quantitative analysis, capillary electrophoresis CAPA-3000 manufactured by Otsuka Electronics
Was used. Example 1-1 In this example, the developer according to the second aspect of the present invention is manufactured. Here, the developer is obtained by further adding carbon black in the method according to the first aspect of the present invention, and is also an example of the first aspect.

Synthesis of Resin Emulsion Styrene: 16 parts n-Butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion-exchanged water: 79 parts The above ammonium persulfate is dissolved in the above ion-exchanged water,
The above polymerizable monomer was added and reacted in a 1 liter four-necked flask at a stirring speed of 250 rpm, a polymerization temperature of 70 ° C. and a polymerization time of 8 hours to obtain a resin emulsion having an average particle diameter of 0.8 μm and a weight average molecular weight of 700 as an oligomer. And its structural formula (n: integer of 1 to 10, R1, R2, R3: carbon number 1
~ 6 alkyl groups)

[0048]

[Chemical 3] Was obtained.

Synthesis of Composite Particles The above resin emulsion: 25 parts The above anionic oligomer: 0.02 part Carbon black: 2 parts Cationic oligomer: 0.5 part Ion-exchanged water: 430 parts The above components are mixed with a stir bar to obtain a dispersion liquid. Got When the miscibility test of this dispersion was conducted, the zeta potential was 30 mV and the dispersion was stable. Next, 10 parts of styrene in which 0.3 part of azobisisobutylnitrile was dissolved was added to this dispersion liquid, and a homogenizer (TK KAU manufactured by Tokushu Kika Kogyo Co., Ltd.) was added.
(TO homo mixer), stirring at 600 rpm for 10 minutes,
The reaction was carried out in a 1 liter four-necked flask at a stirring speed of 80 rpm, a polymerization temperature of 80 ° C., and a polymerization time of 3 hours to obtain an average particle size of 8.
0 μm composite particles were obtained. When the composite property of the composite particles was tested, it was found that the composite particles contained composite components that were composited at a ratio close to the ideal ratio. When the composite particles washed with ion-exchanged water were subjected to a drying test, a moisture content of 0.39%, which was excellent, was found. When this composite particle was subjected to a moisture resistance and water resistance test, it remained at a low value of 0.29% at room temperature and normal humidity and 0.30% even at high temperature and high humidity, and excellent moisture resistance was observed. FIG. 3 shows the results of observing the change in water content for the drying property within the range of 24 hours, 48 hours and 100 hours or more. It can be seen that a drying time of about 24 hours is sufficient.

Further, in the cleanliness test of the cleaning liquid, the oligomer was present in an amount of 10% or more of the charged amount, which was Δ.
The cationic oligomer used above has a weight average molecular weight of 1500 and a structural formula of CH ₂ = CR ₁ COO (CH ₂ ) _n.
-NHR ₂ R ₃ is an acid-base dissociation constant of 10 ⁻³ or less (25
(Value in infinitely diluted solution at ℃).

Since the composite particles can also be used as a toner for electrophotography, a fog test was also conducted, and the fog did not increase even at high temperature and high humidity, showing a low value.
It was also found to be promising as a polymerized toner. Example 1-2 In the same manner as in Example 1-1, except that 13 parts of the following carbon black dispersion liquid was used in place of the carbon black and the cationic oligomer for the synthesis of composite particles, an average particle size of 8.5 μm was obtained. It was The determination of the test result was the same as in Example 1-1.

Filler dispersion Carbon black: 15 parts Cationic oligomer: 4 parts Ion-exchanged water: 100 parts The above raw materials are ball milled (HD pot mill type A-).
3 (manufactured by Knicker) for 10 hours to obtain a carbon black dispersion having an average particle size of 0.2 micron. Example 1-3 Composite particles were obtained in the same manner as in Example 1-1 except that titanium oxide (TiO2) was used in place of carbon black. The determination of the test result was the same as in Example 1-1. The following feldspar powder in Example 1-4 Example _{1-1 (K 2 O · Al 2} O
Composite particles having an average particle size of 8.5 μm were obtained in the same manner except that 5 parts of the ₃ · SiO ₂ ) dispersion was used instead of the carbon black and the cationic oligomer for the synthesis of the composite particles. The determination of the test result was the same as in Example 1-1.

Filler dispersion Feldspar powder (K ₂ O.Al ₂ O ₃ .SiO ₂ ): 10 parts Cationic oligomer: 2 parts Ion-exchanged water: 100 parts The above raw materials are ball milled (HD pot mill typeA-
3 (manufactured by Knicker) for 10 hours to obtain a feldspar powder dispersion having an average particle size of 0.3 micron. Example 1-5 Composite particles were obtained in the same manner as in Example 1-1, except that magnetic powder (FeO ₃ ) was used as the composite filler instead of carbon black, and the average particle size was 9.5 μm. The determination of the test result was the same as in Example 1-1. Comparative Example 1-6 Composite particles having an average particle size of 7.0 μm were obtained in the same manner as in Example 1-1 except that a quaternary aluminum salt was used as the terminal group of the cationic oligomer. As a result of the moisture resistance test, what was 0.30% at room temperature and normal humidity increased to 0.39%,
By changing the polar group of the oligomer to one having a high hydration property, the moisture resistance was adversely affected as compared with Example 1-1. Further, the dryness test and the fogging test were x. Determination of the results of other tests was the same as in Example 1-1. Comparative Example 1-2 As an anionic oligomer having a styrene polymerization derivative structure in place of the cationic oligomer in Example 1-1

[0054]

[Chemical 4] Composite particles were obtained in the same manner except that was used. As a result of the composite property test, the composite ratio remained at 20% of the charged amount, and the composite property was adversely affected as compared with Example 1-1 due to the absence of the cationic oligomer. In addition, other tests could not be conducted because the yield was too low. Comparative Example 1-3 Composite particles were obtained in the same manner as in Example 1-1 except that lauryltrimethylaluminum chloride was used instead of the cationic oligomer. Miscibility test results,
The zeta potential was low and was 7 mV. Due to the hydrophobic portion having a low compatibility with the polymerizable monomer, the miscibility was adversely affected as compared with Example 1-1, aggregation occurred during the polymerization, and polymer particles could not be obtained. Comparative Example 1-4 Composite particles having an average particle size of 6.5 μm were obtained in the same manner as in Example 1-1 except that sodium dodecylbenzenesulfonate was used instead of the anionic oligomer. In the dryness test, the water content after 12 hours was 1.00%, which was very high, and the poor drainage of ordinary surfactants was observed. Regarding the drying property, the result of observing the change of the water content in the range of 24 hours, 48 hours and 100 hours or more is shown in FIG. 3 in comparison with Example 1-1. It can be seen that the drying time is 24 hours in Example 1-1, which is almost double that of 48 hours. Further, FIG. 4 is a graph showing the moisture content with respect to temperature and humidity conditions for Example 1-1 and Comparative Example 1-4. As shown in FIG. 4, as a result of the humidity resistance test, in Example 1-1, it was 0.29% at room temperature and normal humidity and 0.30% at high temperature and high humidity, whereas in this comparative example, it was normal temperature at room temperature. What was 0.40% in humidity increased to 0.55%,
It was found that the moisture resistance was significantly adversely affected by changing the oligomer to a normal surfactant, as compared with Example 1-1. In addition, the cleanability test and the fogging test were both bad. Determination of the results of other tests was the same as in Example 1-1. Example 2-1 This example illustrates the third aspect of the invention.

Synthesis of Resin Emulsion Styrene: 20 parts n-Butyl acrylate: 5 parts Ammonium persulfate: 2 parts Ion-exchanged water: 73 parts The above ammonium persulfate is dissolved in the above ion-exchanged water,
The above polymerizable monomer was added and reacted in a 1 liter four-necked flask at a stirring speed of 250 rpm, a polymerization temperature of 70 ° C. and a polymerization time of 8 hours to obtain a resin emulsion having an average particle diameter of 1.0 μm and a weight average molecular weight as an oligomer. The structural formula (n: integer of 1 to 10; R1, R2, R3: alkyl group having 1 to 6 carbon atoms) is 800.

[0056]

[Chemical 5] An anionic oligomer having an acid-base dissociation constant of 10 ⁻³ or less (value in an infinitely diluted solution at 25 ° C.) was obtained.

Synthesis of Composite Particles The above resin emulsion: 25 parts The above anionic oligomer: 0.02 part Carbon black: 2 parts Cationic oligomer: 0.5 part Self-emulsifying polyethylene wax: 0.5 part Ion-exchanged water: 430 Parts The above was mixed with a stir bar to obtain a dispersion. When a miscibility test was conducted on this dispersion, the zeta potential was 35 mV, indicating that the dispersion was stably dispersed. The pH of this dispersion was adjusted to 3.0 with acrylic acid, then 10 parts of styrene in which 0.3 part of azobisisobutylnitrile was dissolved was added, and a homogenizer (TK Auto homomixer manufactured by Tokushu Kika Kogyo) was added. ) At 6000 rpm for 10 minutes and 1 liter 4
Stirring speed 80 rpm, polymerization temperature 80 in one-necked flask
The reaction was carried out at a polymerization temperature of 3 hours for 3 hours to obtain composite particles having an average particle size of 10 μm. When a compositeness test was conducted, it was found that carbon was contained in the polymer particles and composited at a ratio close to the ideal. When the product washed with ion-exchanged water was subjected to a drying test, a moisture content of 0.37%, which was excellent in drying property, was observed. A drying time of 24 hours was sufficient. When this composite particle was subjected to a moisture resistance and water resistance test, it showed a low value of 0.28% at room temperature and normal humidity and 0.28% at high temperature and high humidity, and excellent moisture resistance was observed. Also, in the cleanability test of the cleaning liquid, the oligomer was 10% or more of the charged amount.
Met. Further, as shown in FIG. 5, the fogging test shows a low value of 3.0% at room temperature and normal humidity and 3.4% at high temperature and high humidity.
It was confirmed that the polymerized toner also has excellent moisture resistance.

The cationic oligomer used above has a weight average molecular weight of 1500 and a structural formula of CH ₂ = CR ₁ COO.
_{(CH 2) n -NHR 2 R} 3 a is acid-base dissociation constant 10
^-3 or less (value in 25 ° C. infinitely diluted solution). The self-emulsifying polyethylene wax used had a weight average molecular weight of 3000 and was neutralized with ammonia. Example 2-2 Composite particles were obtained in the same manner as in Example 2-1, except that the pH was adjusted to 4.0. Example 2 was used to judge the test results.
It was the same as -1. Example 2-3 Composite particles were obtained in the same manner as in Example 2-1, except that the pH was adjusted to 5.0. Example 2 was used to judge the test results.
It was the same as -1. Example 2-4 Composite particles were obtained in the same manner as in Example 2-1, except that the pH was adjusted to 6.0 with aqueous ammonia. The determination of the test result was the same as in Example 2-1. Examples 2-5, 6, 7 8.0 μm except that phthalocyanine blue, benzidine yellow, and permanent rhodamine were used in place of carbon black in Example 2-1.
Composite particles of 7.5 μm and 8.5 μm were obtained. The determination of the test result was the same as in Example 2-1. In particular, in the fogging test, the values were as low as 3.5% at room temperature and normal humidity and 3.8% at high temperature and high humidity, and it was confirmed that the toner has excellent moisture resistance as a color toner. Comparative Example 2-1 Composite particles were obtained in the same manner as in Example 2-1, except that the pH was adjusted to 7.0 with aqueous ammonia. In the miscibility test, it was as low as 8 mV and agglomerated during the polymerization, and other tests could not be performed. Comparative Example 2-2 Composite particles were obtained in the same manner as in Example 2-1 except that PH was adjusted to 2.0. In the miscibility test, it was as low as 5 mV and agglomerated during the polymerization, and other tests could not be performed as in Comparative Example 2-1. Comparative Example 2-3 Average particle size was the same as in Example 2-1, except that polyethylene wax having a molecular weight of 4500 emulsified with an anionic surfactant (sodium dodecylbenzenesulfonate) was used instead of the self-emulsifying polyethylene wax. 7.5 μm composite particles were obtained. In the drying test, the water content after 12 hours was 1.20%, which was very high, and the poor drainage of the usual surfactant was observed. It was found that the drying takes 48 hours, which is almost double that of Example 2-1. Further, as a result of the humidity resistance test, 0.45% at room temperature and normal humidity increased to 0.65%, and by changing the oligomer to a normal surfactant, compared with Example 2-1. It was found that the moisture resistance was significantly adversely affected. Also, cleanability test,
It was x in the fogging test. Regarding the fogging test, FIG. 5 is a graph showing the relationship of fogging with respect to temperature and humidity conditions in Example 2-1 and Comparative Example 2-3. As shown in FIG. 5, it is 4.0% at room temperature and normal humidity, and 12.0 at high temperature and high humidity.
% And fogging increased, and the toner could not pass the moisture resistance test. Determination of the results of other tests was the same as in Example 2-1. Example 3-1 This example illustrates an example of the fourth aspect of the invention.

Synthesis of composite particles Carbon black: 2 parts Cationic oligomer: 0.5 part Ammonium persulfate: 0.01 part Ion-exchanged water: 100 parts The above components were mixed with a stirring bar to obtain a dispersion liquid. When the miscibility test of this dispersion was conducted, the zeta potential was 30 mV and the dispersion was stable. Next, 10 parts of styrene was added to this dispersion and reacted in a 1 liter four-necked flask at a stirring speed of 80 rpm, a polymerization temperature of 70 ° C. and a polymerization time of 3 hours to obtain composite particles having an average particle size of 7.8 μm. . When the composite property of the composite particles was tested, it was found that the composite particles contained composite components that were composited at a ratio close to the ideal ratio. When the composite particles washed with ion-exchanged water were subjected to a drying test, a moisture content of 0.37%, which was excellent in drying property, was observed. A drying time of 24 hours was sufficient. When this composite particle was subjected to a moisture resistance and water resistance test, it was a low value of 0.27% both at room temperature and normal humidity and at high temperature and high humidity, and excellent moisture resistance was observed. In addition, in the cleanness test of the cleaning liquid,
The oligomer was less than 5% of the charged amount, and the residual amount in the waste water was small, and compared to Examples 1-1 and 2-1, improvement in soap-free and cleanliness was observed.

The cationic oligomer used above has a weight average molecular weight of 1500 and a structural formula of CH ₂ = CR ₁ COO.
It was from _{(CH 2) n -NHR 2 R} 3. Also,
Since this composite particle can be used as a toner for electrophotography, when a fogging test was also conducted, it showed a low value with no increase in fogging even at high temperature and high humidity, and was found to be promising as a polymerized toner.

A characteristic feature of this production method is that the decomposed pieces of the reactive emulsifier and the oligomers of opposite polarity are integrated and deposited on the surface of the polymer particles. Since this precipitation occurs in the form of particles, the surface of the polymer particles has the property of being sprinkled with sand of uniform size.
It can be observed with an EM photograph. Polymerization occurs mainly in the aqueous phase rather than on the surface of the particles, and because the polymerization rate is faster than the precipitation rate, the surface properties are as if they were sprinkled with such fine particles. Example 3-2 In Example 3-1, azobisisobutylamidine hydrochloride was used in place of ammonium persulfate, and anionic oligomer having a styrene polymerization derivative structure was used in place of the cationic oligomer of tertiary amine.

[0062]

[Chemical 6] Were used in the same manner as above to obtain composite particles having an average particle size of 8.0 μm. The composite particles were excellent in the humidity resistance test without absorbing moisture at high temperature and high humidity. In the cleanness test, the oligomer was 10% or less of the charged amount, the residual amount in the waste water was small, and soap-free and clean were observed. Other tests were also good. Example 3-3 Composite particles with an average particle size of 6.7 μm were obtained in the same manner as in Example 3-1, except that the composite particles obtained in Comparative Example 1-4 were used instead of carbon black. The composite particles of Comparative Examples 1-4 had poor moisture resistance because a normal surfactant was used during dispersion. However, the composite particles obtained in this example were excellent in the moisture resistance test without absorbing moisture at high temperature and high humidity. In the cleanness test, the oligomer was 10% or less of the charged amount, the residual amount in the waste water was small, and soap-free and clean were observed. Other tests were also good. Example 3-4 Composite particles with an average particle size of 8.5 μm were obtained in the same manner as in Example 3-1, except that quaternary ammonium salt cetyltrimethylammonium bromide was used in place of the tertiary amine cationic oligomer. . The composite particles of Comparative Example 1-1 had poor moisture resistance because of the quaternary ammonium salt. However, the composite particles obtained in this example were excellent in the moisture resistance test without absorbing moisture at high temperature and high humidity.
In the cleanness test, the oligomer was 10% or less of the charged amount, the residual amount in the waste water was small, and soap-free and clean were observed. Other tests were also good. Example 3-5 Composite particles having an average particle size of 9.5 μm were obtained in the same manner as in Example 3-1, except that titanium oxide (TiO ₂ ) was used instead of the following carbon black. The determination of the test result was the same as in Example 3-1. Example 3-6 Composite particles having an average particle size of 10.0 μm were obtained in the same manner as in Example 3-1, except that alumina (Al ₂ O ₃ ) was used instead of the following carbon black. The determination of the test result was the same as in Example 3-1. Comparative Example 3-1 Composite particles having an average particle size of 9.5 μm were obtained in the same manner as in Example 3-1, except that azobisisobutylamidine hydrochloride was used instead of ammonium persulfate. Since the decomposed segment of the reactive initiator and the oligomer have polar groups with the same sign, in the cleanability test, the oligomer was less than 20% of the charged amount, and the residual amount in the wastewater was large. Other tests were good. Example 4-1 This example illustrates an example of the fourth aspect of the invention.

Synthesis of composite particles Carbon black: 2 parts Cationic oligomer: 0.5 part Self-emulsifying polyethylene wax: 0.5 part Ammonium persulfate: 0.01 part Ion-exchanged water: 100 parts The above are mixed with a stirring bar. The dispersion was adjusted to pH 3.0 with acrylic acid. When the miscibility test of this dispersion was conducted, the zeta potential was 32 mV and the dispersion was stable. Next, 10 parts of styrene was added to this dispersion, and the mixture was reacted in a 1 liter four-necked flask at a stirring speed of 80 rpm, a polymerization temperature of 70 ° C., and a polymerization time of 3 hours to obtain an average particle size of 9.0 μm.
m composite particles were obtained. When a composite property test was conducted, it was found that the composite particles contained the composite components at a ratio close to the ideal, and were composited. When the product washed with ion-exchanged water was subjected to a drying test, the water content was 0.38%, which was excellent. When the composite particles were subjected to a moisture resistance and water resistance test, both room temperature and normal humidity and high temperature and high humidity remained at low values of 0.29%, and excellent moisture resistance was observed. When a fogging test was carried out, it was found that fogging did not increase even at high temperature and high humidity, and that the polymerized toner also had excellent moisture resistance. In addition, in the cleanness test of the cleaning liquid,
The oligomer was less than 5% of the charged amount, and the residual amount in the waste water was small, and soap-free and clean were observed.

The cationic oligomer used above has a weight average molecular weight of 1500 and a structural formula of CH ₂ = CR ₁ COO.
It was from _{(CH 2) n -NHR 2 R} 3. The self-emulsifying polyethylene wax used had a weight average molecular weight of 3000 and was neutralized with ammonia. Example 4-2 Composite particles were obtained in the same manner as in Example 4-1, except that the pH was adjusted to 4.0. The result of the test is determined in Example 4
It was the same as -1. Example 4-3 Composite particles were obtained in the same manner as in Example 4-1, except that the pH was adjusted to 5.0. The result of the test is determined in Example 4
It was the same as -1. Example 4-4 Composite particles were obtained in the same manner as in Example 4-1, except that the pH was adjusted to 6.0 with aqueous ammonia. The determination of the test result was the same as in Example 4-1. Examples 4-5, 6, 7 9.0 μm except that phthalocyanine blue, benzidine yellow, and permanent rhodamine were used in place of carbon black in Example 4-1.
Composite particles of 8.5 μm and 9.5 μm were obtained. The determination of the test result was the same as in Example 4-1. In particular, in the fogging test, it was confirmed that the moisture resistance was 3.2% at room temperature and normal humidity and 3.5% at high temperature and high humidity, which was excellent as a color toner. Comparative Example 4-1 Composite particles were obtained in the same manner as in Example 4-1, except that the pH was adjusted to 7.0 with aqueous ammonia. In the miscibility test, it was as low as 8 mV and agglomerated during the polymerization, and other tests could not be performed. Comparative Example 4-2 Composite particles were obtained in the same manner as in Example 4-1 except that PH was adjusted to 2.0. In the miscibility test, it was as low as 6 mV, and agglomeration occurred during the polymerization, and other tests could not be performed as in Comparative Example 2-1. Comparative Example 4-3 Average particle diameter was the same as in Example 4-1, except that polyethylene wax having a molecular weight of 4500 emulsified with an anionic surfactant (sodium dodecylbenzenesulfonate) was used instead of the self-emulsifying polyethylene wax. 8.5 μm composite particles were obtained. In the dryness test, the water content after 12 hours was 0.95%, which was very high, and the poor drainage of the usual surfactant was observed. It was found that the drying takes 48 hours, which is almost double that of Example 4-1. In addition, as a result of the humidity resistance test, what was 0.40% at room temperature and normal humidity increased to 0.55%, and by changing the oligomer to a normal surfactant, compared with Example 4-1. The moisture resistance was adversely affected. In addition, the cleanability test and the fogging test were both bad. Regarding the fogging test, the fog increased to 4.0% at room temperature and normal humidity and 10.0% at high temperature and high humidity, and the humidity resistance test as a toner could not be cleared. Determination of the results of other tests was the same as in Example 4-1.

The test results of the above examples are summarized below. Miscibility Complexity Dryability Moisture resistance Cleanability Fog test Example 1-1 ○ ○ ○ ○ △ ○ Example 1-2 ○ ○ ○ ○ △ △ ○ Example 1-3 ○ ○ ○ ○ △ ○ Example 1-4 ○ ○ ○ ○ △ ○ Example 1-5 ○ ○ ○ ○ △ ○ Comparative Example 1-1 ○ ○ × × △ × Comparative Example 1-2 ○ × − − − − Comparative Example 1-3 × − − − − − − Comparative Example 1-4 ○ ○ × × × × Example 2-1 ○ ○ ○ ○ △ △ ○ Example 2-2 ○ ○ ○ ○ △ ○ Example 2-3 ○ ○ ○ ○ △ ○ Example 2-4 ○ ○ ○ ○ △ ○ Example 2-5 ○ ○ ○ ○ △ ○ Example 2-6 ○ ○ ○ ○ △ ○ Example 2-7 ○ ○ ○ ○ △ ○ Comparative Example 2-1 × − − − − − − Comparison Example 2-2 × − − − − − Comparative Example 2-3 ○ ○ × × × × Example 3-1 ○ ○ ○ ○ ○ ○ Example 3-2 ○ ○ ○ ○ ○ ○ Example 3-3 ○ ○ ○ ○ ○ Example 3-4 ○ ○ ○ ○ ○ ○ Example 3-5 ○ ○ ○ ○ ○ ○ Example 3-6 ○ ○ ○ ○ ○ ○ Comparative Example 3-1 ○ ○ ○ ○ × ○ Example 4-1 ○ ○ ○ ○ ○ ○ Example 4-2 ○ ○ ○ ○ ○ ○ Example 4-3 ○ ○ ○ ○ ○ ○ Example 4-4 ○ ○ ○ ○ ○ ○ Example 4-5 ○ ○ ○ ○ ○ ○ ○ Example 4-6 ○ ○ ○ ○ ○ ○ Example 4-7 ○ ○ ○ ○ ○ ○ Comparative example 4-1 × − − − − − Comparative example 4-2 × − − − − − Comparative example 4-3 ○ ○ XXXXX In the above, in Examples 1-1 to 4-7 and Comparative Examples 1-1 to 4-3, the composite filler was added in the aqueous dispersion, but the present invention is not limited to this. However, the resin particles can be produced without adding a filler.

[0066]

According to the first and second aspects of the present invention,
By defining the terminal group and the hydrophobic part of the oligomer as a means, it becomes effective for the compounding of the resin and the filler component in addition to the usual dispersing action, and as a result, the moisture resistance and water resistance of the composite particles can be made excellent. .

In the third aspect of the present invention, composite particles excellent in moisture resistance are produced by dispersing and complexing a resin, a colorant and a wax with a specific PH in addition to the oligomer defined in the first aspect. it can. In particular, as the polymerized developer, one having excellent moisture resistance in both monochrome and color can be obtained.

In the fourth aspect of the present invention, the reactive emulsifier and the oligomer are integrated and deposited as a hydrophobic substance on the polymerized particles, whereby composite particles excellent in moisture resistance and water resistance can be produced, and soap for drainage is prepared. Freedom and pollution-free can be further improved.

In the fifth embodiment of the present invention, the reactive emulsifier and the oligomer are integrated with each other and the hydrophobic substance is deposited at the specific pH on the polymer particles in which the colorant and the wax are complexed to form a composite having excellent moisture resistance. The particles can be produced, and the soap-free and pollution-free drainage can be further improved. In particular, as the polymerized developer, it is possible to obtain a high-temperature, high-humidity, high-moisture resistance without fogging in both monochrome and color.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing the structure of an oligomer used in the present invention.

FIG. 2 is a model diagram showing a state of an oligomer having a reverse polarity and the decomposition section of the reactive emulsifier used in the present invention.

FIG. 3 is a graph showing the relationship between the drying time and the water content regarding the examples of the first and second aspects of the present invention.

FIG. 4 is a graph showing a relationship between environmental conditions and water content regarding another example of the first and second aspects of the present invention.

FIG. 5 is a graph showing a relationship between environmental conditions and water content regarding an example of a third aspect of the present invention.

FIG. 6 is a color image forming apparatus capable of using the developer according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Photosensitive member 2 ... Charging device 3 ... Exposure device 4 ... Developing device 5 ... Transfer device 6 ... Transfer material 7 ... Fixing device 8 ... Cleaning device 9 ... Eliminating device 10 ... Cleaning blade 200 ... Developing device 201 ... Photosensitive member 202 ... Charging device 203 ... Laser exposure device 204 ... Blade cleaning device 205 ... Static elimination lamp 209 ... Transfer device 210 ... Fixing device 211 ... Heating roller 212 ... Pressure roller 213 ... Image support 214 ... Heater lamp 215 ... Release agent coating member 216 ... Cleaning blade 301 ... Counter ion 302 ... End group 303 ... Hydrophobic part 401 ... Oil phase 402 ... Water phase 403 ... Reactive emulsifier decomposition fragment 404 ... Reverse polarity group oligomer 405 ... Integral hydrophobic material 403 and 404 ... hydrophobic fine particles 407 ... composite particles 408 ... of monomers Swelling pathway

Claims (5)

[Claims] 1. A polymerizable monomer and a resin emulsion,
A method for producing resin particles, which comprises polymerizing an aqueous dispersion containing a hydrophobic part consisting of a monomer skeleton in the repeating structure of the resin and an oligomer having the same hydrophobic part. 2. A polymerizable monomer and a resin emulsion,
A method for producing a developer, which comprises polymerizing an aqueous dispersion containing an oligomer having a hydrophobic part which is the same as a hydrophobic part composed of a monomer skeleton in the repeating structure of the resin, and a colorant. 3. A polymerizable monomer and a resin emulsion,
An aqueous dispersion containing an oligomer having the same hydrophobic part as the monomer skeleton in the repeating structure of the resin, a coloring material, and a self-emulsifying emulsion wax is added.
A method for producing a developer, comprising the step of polymerizing with H3 to H6. 4. A resin comprising a step of polymerizing an aqueous dispersion containing a polymerizable monomer, a reactive emulsifier, and an oligomer having a polar group opposite in polarity to a polar group of a decomposed segment of the reactive emulsifier. Method for producing particles. 5. A polymerizable monomer, a reactive emulsifier, an oligomer having a polar group having a polarity opposite to that of the polar group of the decomposed segment of the reactive emulsifier, a colorant, and a self-emulsifying emulsion wax. A method for producing a developer, comprising a step of polymerizing an aqueous dispersion at pH 3 to 6.