JP3250907B2 - Micron-sized polymer particles and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing micron-sized polymer particles, and more particularly to a micron-sized polymer toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a heating element. The present invention relates to a method for producing conductive plastic particles.

[0002]

2. Description of the Related Art Conventionally, in the field of electrophotographic toner,
Multilayer polymer particles in which a filler such as an inorganic substance is compounded as a third component and contained in a polymer particle comprising a resin and a colorant are known. As a method of producing the multilayer polymer particles, as an example using submicron fine particles which can be easily produced by a general polymerization method, a third method utilizing heteroaggregation or the like is used.
A component compounding technique is known (JP-A-4-5706).
3). However, according to this method, the third component is included in the particle bonding portion due to agglomeration, and it has been difficult to simultaneously satisfy granulation to a micron size and layer formation.

Further, encapsulation by a seed polymerization method or the like, which realizes the formation of micron-sized particles in a single-stage process (Japanese Patent Application Laid-Open Nos. 57-24369 and 60-25820).
3) and core-shell technology (JP-A-62-61632 and JP-A-2-81052) are also known. But,
In the electrophotographic toner obtained by these methods, the surface of the particles is covered with a shell having a high hardness and a high softening point in order to improve the frictional properties, so that the friction resistance can be improved while maintaining the low-temperature fixability. Did not. In addition, because of the polymerization method, moisture resistance as environmental resistance was also a problem.

On the other hand, in the case of the conductive toner and the conductive plastic particles, it is ideal for the added conductive material to be uniformly localized on the surface in order to exhibit the conductive function. It is necessary to add a large amount of a conductive substance in order to exhibit conductivity due to aggregation of the conductive substance. However, in such a case, there is a problem that the fixing temperature of the conductive toner increases. In addition, in the case of conductive plastics, water resistance, moisture resistance, and environmental resistance, which are inconsistent with exhibiting conductivity, were also problems.

Conventionally, as a method for producing irregularly shaped polymer particles containing the third component, a method for producing grape-like polymer particles by an agglomeration method (JP-A-63-186253, JP-A-2-18776).
8), a process for producing spinous polymer particles (JP-A-62-2665)
58), however, the particles obtained by these methods have a weak adhesive force on the adhesive surface, and have a problem in friction resistance due to mechanical stress.

[0006] As a method of deforming by a polymerization method that basically forms a sphere, a surface-depressed polymer particle that is deformed by mixing an organic solvent with an oil phase and volatilizing the organic solvent during polymerization (Japanese Patent Laid-Open No. 1-100562, JP-A-1-30
9070), however, this method has a problem of safety due to volatilization of an organic solvent and a problem of residual odor.

On the other hand, in the electrophotographic toner, the toner formed by the polymerization method generally has a spherical shape, which has a problem of adversely affecting the cleaning property. There were also problems with respect to environmental resistance, such as a decrease in friction and a decrease in moisture resistance due to a polymerization method.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing micron-sized multilayer polymer particles which has solved the above-mentioned problems.

More specifically, an object of the present invention is to firstly provide a low-temperature fixing polymerized toner having excellent friction resistance. Another object of the present invention is to provide a method for producing micron-sized irregularly shaped polymer particles that solves the above-mentioned problems, and secondly, to provide an irregularly shaped polymerized toner having excellent cleaning properties.
Third, the above-mentioned problems are solved by the method for producing irregularly shaped polymer particles and the method for producing multilayer polymerized particles of the present invention, and a low-temperature fixable polymerized toner having excellent cleaning properties and excellent rubbing resistance despite irregular shapes is provided. It is an object. Fourth, a low-temperature-fixing conductive polymer toner that has solved the above-mentioned problems by the method for producing multilayer polymer particles of the present invention. Fifth, highly durable conductive polymer planar heat generation by conductive plastic particles having excellent moisture resistance. It is intended to provide the body. It is another object of the present invention that the first to third polymerized toners have excellent moisture resistance.

[0010]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and is constituted by the following first to fifth inventions.

The first invention (Claim 1) provides a dispersion liquid comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles and a filler. ,
The polymerizable monomer, the resin particles and the filler are granulated and integrated by applying a shear flow or a stirring flow, and are subjected to a polymerization reaction to produce micron-sized multilayer polymer particles having a filler layer containing the filler on the surface. Wherein the polar group of the resin particles in the dispersion and the polar group of the dispersant of the filler have opposite polarities, and the particle diameter R _{A of the} resin particles.
And the particle diameter R _{B of the} filler are (R _A + R _B ) ² / R _B
^{The present} invention provides a method for producing micron-sized multilayer polymer particles, wherein the relationship of ² > 121 is satisfied, and the hydrophobic part of the resin particles and the hydrophobic part of the dispersant of the filler have an unsaturated double bond. In the method, in order to obtain a polymerized toner having a filler layer, the resin particles are thermoplastic resin particles containing a colorant, and the polar group of the resin particles and the polar group of the filler are weakly acidic groups and weakly basic groups, respectively. Should be fine.

A second invention (claim 2) provides a dispersion liquid comprising a dispersion medium containing water and a polymerizable monomer having an unsaturated double bond, and a dispersoid containing particles A and B. The micron-sized multilayer polymer particles having at least one depression on the surface by subjecting the polymerizable monomer, particles A and particles B to granulation and integration by applying a shear flow or a stirring flow, and causing a polymerization reaction. Comprising the steps of producing particles A
And the polar group of the dispersant of the particle B are opposite polarities,
The particle diameter _{R B} of the particle diameter _{R A} and particles B of particles A, (R
Satisfy the relationship of ^{_{A + R B) 2 / R}} B 2> 121, the particles A
Ρ _A , the specific gravity ρ _{B of} the particles _B , the weight W _{A of} the particles _A , and the weight WB of the particles _B are 4.0 <W _A /
_{W B) × (ρ B /} ρ A) to provide a method for manufacturing a profiled polymerization micron-sized particles, characterized by satisfying the 7.5 relationship.

In the above method, in order to obtain an irregularly polymerized toner, the particles A are resin particles, the particles B are colorants having a dispersant on the surface thereof, and the polar group of the particles A and the dispersant of the particles B It is only necessary that the polar groups are a weakly acidic group and a weakly basic group, respectively, and that the hydrophobic part of the particle A and the hydrophobic part of the dispersant of the particle B have an ethylenically unsaturated double bond.

According to a third aspect of the present invention, there is provided a dispersion comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles and a filler. ,
The polymerizable monomer, the resin particles and the filler are granulated and integrated by applying a shear flow or a stirring flow, and a polymerization reaction is carried out, whereby a filler layer containing the filler on the surface and a micron having at least one depression portion are provided. a method of manufacturing a size multilayered polymer particles, the polar group the polar group and filler dispersant having the resin particles is opposite polarity, and the particle diameter R _B of the particle diameter R _a filler of the resin particles, satisfy the relationship of ^{_{(R a + R B) 2}} / R B 2> 121, a specific gravity [rho _a of resin particles, a filler having a specific gravity [rho _B, the weight W _a of resin particles, and filler - weight W _B is 4.0 <
(W _A / W _B ) × (ρ _B / ρ _A ) <5.0 and 6.0 <
(W _A / W _B ) × (ρ _B / ρ _A ) <7.5, and the hydrophobic portion of the resin particles and the hydrophobic portion of the filler dispersant have an unsaturated double bond. The present invention provides a method for producing micron-sized irregularly-shaped and multilayered polymer particles characterized by the following.

In the above method, in order to obtain a deformed / multilayer polymerized toner, the resin particles are summer plastic resin particles, and the polar group of the resin particles and the polar group of the dispersant of the filler are weakly acidic groups and weakly acidic groups, respectively. Any basic group may be used.

According to a fourth aspect of the present invention, there is provided a dispersion comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles and a conductive substance. The liquid, the polymerizable monomer, resin particles and a conductive substance are granulated and integrated by applying a shear flow or an agitation flow, and a polymerization reaction is performed, thereby having a conductive layer containing the conductive substance on the surface. A method for producing micron-sized multilayer polymer particles, comprising a polar group of resin particles and a dispersant for a conductive substance .
Of the polar group are opposite polarity, and the particle diameter _{R B} of the particle diameter _{R A} and conductive substance of the resin ^{_{particles, (R A + R B)}} 2 / R
_B ² > 121, and the specific gravity ρ _{A of the} resin particles,
Specific gravity ρ _B of the conductive substance, specific gravity ρ _M of the polymerizable monomer,
Weight _{W A} of the resin particles, the weight _{W B} of the electrically conductive material, and the weight _{W M} of the polymerizable monomer, 1.0 _<W M /
_{ρ M) / (W A /} ρ A + W B / ρ B) <3.
0, wherein the resin particles are a thermoplastic resin, and the hydrophobic part of the resin particles and the hydrophobic part of the dispersant of the conductive substance have an unsaturated double bond. And a method for producing the same.

A fifth invention (claim 5) comprises a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles, and a conductive substance. By applying a shear flow or a stirring flow to the dispersion, the polymerizable monomer, the resin particles, and the conductive material are granulated and integrated,
By a polymerization reaction, a method for producing micron-sized multilayer polymer particles having a conductive layer containing the conductive substance on the surface of the polymer particles, wherein the polar group of the resin particles and the polar group of the dispersant of the conductive substance are a reverse polarity, and the particle diameter R _B of the particle diameter R _a and conductive substance of the resin particles, (R a ₊ R
^{_{B) 2 / R B 2>}} 121 satisfy the relationship of the specific gravity [rho _A of the resin particles, the specific gravity [rho _B of the conductive material, the specific gravity [rho _M of the polymerizable monomer, the weight _{W A} of the resin particles, the conductive material Weight W
_B, and the weight _{W M} of the polymerizable monomer, 1.0 <W
_{M / ρ M) / (W} A / ρ A + W B / ρ B)
<3.0, the hydrophobic part of the resin particles and the hydrophobic part of the dispersant of the conductive substance have an unsaturated double bond, the polar group of the resin particles is a weakly acidic group, and Provided is a method for producing conductive plastic particles, wherein the polar group of the dispersant for a conductive substance is a weakly basic group.

[0018]

In the method for producing micron-sized multilayer polymer particles according to the first aspect of the present invention, the dispersion containing the polymerizable monomer, the resin particles A, and the filler B is subjected to a shear flow or a stirring flow to form granules. And then polymerize. In this case, when the particles A and B have opposite polarities and the particle diameters are R _A and R _B (R
^{_{A + R B) 2 / R}} B 2> to have 121 a is the particle diameter difference, i.e. the resin particles have opposite polarity greater than the filler particles, and the particles A, the hydrophobic part of the hydrophobic portion or dispersant B is not It is necessary to have a saturated double bond.

Under such conditions, the hetero-aggregation of the resin particles A and the filler particles B, the compatibility between the polymerizable monomer and the particles A and B, the swelling of the resin particles, and the granulation of the fillers are reduced. It is believed that polymer particles having a micron-sized filler layer can be produced. The conditions for the particle size difference were determined by experiments.

That is, the particles A and the particles B are integrated by heteroaggregation, and the one in which the reactive monomer swells is
Particles A and B, which have been granulated by an appropriate shear flow to be micron-sized and hetero-aggregated, have increased swelling amount of the reactive monomer, so that particles B are separated by hydrophobic force due to a difference in hydrophilicity. Then, movement to the oil-water interface occurs and the filler
It is believed that a layer is formed.

According to the first aspect, a polymerized toner as shown in FIG. 1 can be obtained. This polymerized toner has excellent abrasion resistance because it has a filler layer 102 containing a filler 101 on its surface, and has low-temperature fixability because the resins 103 and 104 are thermoplastic resins having a low softening point. Are better.

In the case of producing the polymerized toner shown in FIG. 1, the coloring property of the toner is imparted by the fact that the particles A contain a coloring agent, and the resin particles are made of a low-polymer having the same composition as the polymerizable monomer. By forming the softening point thermoplastic resin particles, the toner is given low-temperature fixability, and the filler containing filler can be used.
The formation of the layer imparts abrasion resistance to the toner. Further, by making the polar group of the particles A and B a weakly acidic group or a weakly basic group, and making the hydrophobic part have the same skeletal structure as the polymerizable monomer, for example, the dispersant of the filler B can be used. An oligomer or the like imparts moisture resistance.

In the method for producing micron-sized irregularly polymerized particles having surface depressions according to the second invention, a shear flow or a stirring flow is applied to a dispersion containing a polymerizable monomer, particles A and particles B. And then polymerized. In this case, it is necessary that the particles A and B have opposite polarities and the particle A has a particle size larger than B in order to granulate to a micron size. ratio _{4.0 <(W a / W B} ) * (ρ B / ρ a) it is necessary <7.5.

Under such conditions, it is considered that by effectively coagulating the resin particles and the particles, polymer particles having a micron size and having a depression on the surface can be produced. Further, the deforming and the mixing ratio of particles A and B have the following relationship.

(1) 5.0 <(W _A / W _B ) × (ρ _B /
ρ _A ) <6.0 As shown in FIG. 2 (a), the degree of deformation becomes stronger.

(2) 4.0 <(W _A / W _B ) × (ρ _B /
_{ρ A) <5.0 6.0 <(} W A / W B) × (ρ B / ρ A) <7.5 , as shown in FIG. 2 (b), the degree of profiled becomes weak.

(3) 2.0 <(W _A / W _B ) × (ρ _B /
_{ρ A) <4.0 7.5 <(} W A / W B) × (ρ B / ρ A) <8.5 , as shown in FIG. 2 (c), spheronized.

The above numerical conditions are obtained from experiments.

According to the second aspect of the invention, it is possible to obtain a modified polymer toner having a depression on the surface as shown in FIG.
This toner has excellent cleaning properties.

Further, in order to produce a polymerized toner,
Particle A is a resin particle having the same composition as the polymerizable monomer, Particle B is a colorant having on its surface a dispersant having the same skeleton structure as the polymerizable monomer, and Particle A and Particle B By making the polar group a weakly acidic group or a weakly basic group, for example, by using a dispersant for the colorant as an oligomer, coloring property and moisture resistance are imparted.

The micron-sized variant according to the third invention
In the method for producing multilayer polymerized particles, a dispersion containing a polymerizable monomer, resin particles A, and filler B is first subjected to a shear flow or a stirring flow to granulate, and then polymerized. In this case, as in the first invention, the resin particles are larger and opposite in polarity than the filler particles, and the hydrophobic portion of the particles A and B or the hydrophobic portion of the dispersant has an ethylenically unsaturated double bond. Polymer particles having a filler layer are produced.

In order to have both the depressed portion and the filler layer and not adversely affect the friction resistance, the mixing ratio of the particles A and B is set to 4.0 <(W _A / W _B ) × (ρ _B / Ρ _A ) <5.
0 and 6.0 <(W _A / W _B ) × (ρ _B / ρ _A ) <
It needs to be 7.5. This means that by adjusting the degree of irregularity to be within this range, it is possible to effectively exhibit the abrasion resistance of the filler layer as well as the irregular shape.
The numerical conditions were obtained from experiments.

According to the third aspect, a polymerized toner as shown in FIG. 3 can be obtained. Since this polymerized toner has a depressed portion 301 on its surface, it has excellent cleaning properties and has a filler layer 3 containing a filler 302 on its surface.
03, so that it has excellent wear resistance,
Since 04 and 305 are low softening point resins, they have excellent low-temperature fixability.

Further, in order to obtain the polymerized toner shown in FIG. 3, it is sufficient that the particles A contain thermoplastic resin particles having a low softening point and the same composition as the polymerizable monomer.
Thereby, coloring property and low-temperature fixing property as a toner are imparted. Filler B is added for abrasion resistance,
Since the hydrophobic part of the particles A and B or the hydrophobic part of the dispersant has an ethylenically unsaturated double bond and the polar group is a weakly acidic group or a weakly basic group, the moisture resistance of the toner is imparted. I have.

According to the method for producing micron-sized multilayer polymer particles having a conductive layer on the surface according to the fourth invention, the dispersion containing the polymerizable monomer, the resin particles A and the conductive material B is
Granulation is performed by applying a shear flow or a stirring flow, and then polymerization is performed. In this case, as in the first invention, the particle size of the resin particles is larger than that of the conductive substance and has opposite polarity, and the hydrophobic portion of the particles A and B or the hydrophobic portion of the dispersant has an ethylenically unsaturated double bond. , Agglomeration between the resin particles and the conductive material due to hetero-aggregation of the resin particles and the conductive material, compatibility between the polymerizable monomer and the particles A and B, and swelling, and the micron size It is considered that polymer particles having a conductive layer can be produced by the above method.

According to the fourth aspect, a conductive polymerized toner as shown in FIGS. 4A to 4C can be obtained. The conductive polymer toner is mainly composed of a resin 403 having on its surface a conductive layer 402 in which a conductive substance 401 is localized.

Further, in order to produce the conductive polymer toner shown in FIG. 4, the shape of the conductive polymer toner can be varied from spherical to irregular depending on the mixing ratio of the particles A and B, as in the second invention. It is. Further, the polymerizable monomer, particles A, the blending ratio of _{B 1.0 <(W M, ρ} M) / (W A / ρ A + W B /
By setting ρ _B ) <3.0, the conductivity is adjusted so that the conductivity can be effectively exhibited. The conditions are obtained from experiments. Further, in order to produce a low-temperature fixing conductive toner, the resin of the particles A may be a resin having a low softening point.

According to a fifth aspect of the present invention, there is provided a method for producing polymer particles of conductive plastic having a conductive layer, which is a multilayer polymer particle having a micron size, comprising a dispersion containing a polymerizable monomer, resin particles A and a conductive substance B. The liquid is granulated by subjecting it to a shear flow or a stirring flow, and then polymerized. in this case,
As in the first invention, the particle size of the resin particles is larger than that of the conductive material and opposite in polarity, and the hydrophobic portion of the particles A and B or the hydrophobic portion of the dispersant has an ethylenically unsaturated double bond. By having the same, the resin particles and the conductive substance are heteroaggregated, and the compatibility between the polymerizable monomer and the particles A and B and the swelling property cause granulation between the resin particles and between the conductive substances. It is considered that polymer particles having a conductive layer can be produced.

According to the fifth aspect of the present invention, it is possible to obtain conductive plastic particles having a conductive layer 402 in which a conductive substance 401 is localized as shown in FIG.

Further, in order to produce the conductive plastic particles shown in FIG. 4, particles A, B
The shape of the conductive plastic particles can be varied from a spherical shape to an irregular shape depending on the compounding ratio. However, when the conductive plastic particles are applied to a planar heating element, a true spherical shape as shown in FIG. 4C is more effective. . Presumably, the filling property in forming a sheet is related to the shape. Further, the compounding ratio of the polymerizable monomer and the particles A and B is set to 1.0 <(W _M ,
ρ _M) / (W With _{A / ρ A + W B /} ρ B) <3.0, can be adjusted so as to be effectively exhibit conductivity. These conditions were obtained from experiments.

[0041]

The present invention will be described more specifically with reference to the following examples.

The polymerizable monomers used in the present invention include vinyl aromatic monomers, acrylic monomers, vinyl ester monomers, vinyl ether monomers, diolefin monomers, and monoolefins. And the like.

Among them, the monovinyl aromatic monomer includes monovinyl aromatic hydrocarbons such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene, o-, m-, p-chlorostyrene, A single or a combination of two or more of p-ethylstyrene and divinylbenzene can be exemplified.

The acrylic monomers include, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid. 2-ethylhexyl acid, ethyl β-hydroxyacrylate, propyl γ-hydroxyacrylate, butyl δ-hydroxyacrylate, ethyl β-hydroxymethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, etc. Can be mentioned.

The vinyl ester monomers include, for example, vinyl formate, vinyl acetate, vinyl propionate and the like, and the vinyl ether monomers include, for example, vinyl methyl ether, vinyl ethyl ether, vinyl-n-butyl ether, vinyl phenyl Ethers, vinylcyclohexyl ethers and the like, diolefin-based monomers such as butadiene, isoprene, chlorobrene and the like; monoolefin-based monomers such as ethylene, propylene, isobutylene, butene-1, butene-1, 4 -Methylbenthene-1 and the like.

The dispersant used in the present invention includes a hydrophobic portion having a repeating structure of the above-mentioned polymerizable monomer alone or a copolymer of two or more copolymer skeletons, a terminal group, and a weak acid as a polar group.
It has a polar group of a weak base. As an oligomer, for example, anionic fatty acid salt type —COONH ₄
Etc., -OSO ₃ NH ₄ and the like of the sulfate type, -OSO ₃ phosphate ester salt type having an end group such as (NH _{4) 2,} 1,2,3 alkylamine amine salts type cationic , 1, 2, and tertiary ethanols, polyethylene polyamines, etc., and ethylene oxide adducts of alkylamines which are polarized by weak hydration in water and exhibit weak cationic properties.

In order to improve moisture resistance and water resistance, it is desirable to neutralize amines with a relatively weakly acidic lower fatty acid such as formic acid or acetic acid. As a specific example,
CH ₂ = (CH ₂ ) for those having a styrene derivative structure
_n -CH- ◎ -COONH _{4, etc., CH 2 = CR 1 COO (} CH 2) are those having an acrylic _acid derivative structural _n -N
For those having a styrene acrylic acid copolymer derivative structure such as R ₂ R ₃ , CH ₂ ＣＲCR ₁ COO (CH ₂ ) _n CH
₂ =-◎ -OSO ₃ NH _{4 and the} like.
In the above chemical formula, n is an integer of 1 to 10, R ₁ ,
R ₂ and R ₃ each represent an alkyl group having 1 to 6 carbon atoms.

In addition to the above, there may be mentioned itaconic acid derivatives, maleic acid derivatives, fumaric acid derivatives, allyl alcohol derivatives, succinic acid derivatives, urethane derivatives, styrene-maleic acid resins, and half esters thereof. In addition, it is desirable to select a substance having high volatility such as ammonium ion or amine ion, or acetic acid or formic acid, which is a weak acid, for the purpose of neutralization in terms of moisture resistance and water resistance.

The dispersants used in the present invention are not limited to those described above. In addition, the molecular weight of the hydrophobic portion is not limited to the formation of associated micelles as in the case of a normal emulsifier, but becomes a micelle by itself. One hundred to several tens of thousands, particularly 3000 to 15,000 are suitable. The amount of the dispersant used is 0.01 to 30% by weight of the solid content, and preferably 0.1 to 30% by weight, since the effect of moisture resistance and water resistance due to the residual is less than that of ordinary emulsifiers, surfactants and polymer electrolytes. １５15% by weight.

Examples of the polymerization initiator used in the present invention include azo compounds such as azobisisobutyronitrile, cumene hydroperoxide, dicumyl peroxide, and benzoyl peroxide as oil-soluble initiators soluble in monomers. And peroxides such as lauroyl peroxide. In addition, as reactive emulsifiers and reactive surfactants, ammonium persulfate, sodium persulfate whose decomposed sections are anionic,
Persulfates such as potassium persulfate, DE that is cationic
AM (N, N'-diethylaminoethyl methacrylate)
G), AIBN · 2HCl (isobutylamide hydrochloric acid), and the like.

Other examples of the polymerization initiator include polyoxyethylene methacrylate, dimethylaminoethyl, and acetate of diethylaminoethyl methacrylate. Also in this case, by selecting a highly volatile ion such as an ammonium ion or an amine ion as the counter ion, the moisture resistance and the water resistance can be further improved. The amount of the polymerization initiator used is 0.01 to the polymerizable monomer in order to completely polymerize the polymerizable monomer.
10 to 10% by weight, preferably 0.1 to 5% by weight.

The resin particles and the resin particles having a low softening point used in the present invention can be obtained by soap-free emulsion polymerization of the above-mentioned polymerizable monomers used alone or in combination of two or more 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 can be mentioned.

The molecular weight of the resin particles is 1 in weight average molecular weight.
10,000 to 100,000, preferably 10,000 to 50,000 is suitable. The size is in the range of submicron to 1.5 micron in average particle diameter, preferably 0.5 to 1.0 micron. The softening point of the thermoplastic resin is 120 ° C. or less for a monochrome toner and 100 ° C. for a color toner.
C or lower is desirable.

As the filler used in the present invention, iron oxide (FeO ₃ ), alumina (Al ₂ O ₃ ), magnesium oxide (MgO), titanium oxide (TiO ₂ ), oxide Zinc (ZnO), NiO,
SnO, TiBaO ₃ , CeO ₂ , SrTiO ₃ , Cr
In addition to metal oxides such as O, tin oxide, indium oxide, and cerium oxide, fatty acid metal salts such as zinc stearate, calcium stearate, and lead stearate; inorganic substances such as basic bismuth acetate; and PMMA and styrene as organic fillers. -Fluoropolymers such as acrylic copolymers, vinylidene fluoride, and tetrafluoroethylene;

Further, silicic acid, silicates such as SiO ₂ (eg, silica), calcium silicate, aluminum silicate (eg, clay), magnesium silicate (eg, talc, mica, attapulgite), and carbonates such as CaCO ₃ , Ni
As sulfates such as CO ₃ , RaCO ₃ , zirconium and strontium carbonates, barium (BaS)
O ₄ ), gypsum (CaSO ₄ ), etc.
g (OH) ₂ , Mn (OH) ₂ , hydroxide of barium and the like, and other chlorides such as lead (second), glass, metal, fiber and the like can also be mentioned. These fillers may be those subjected to a surface hydrophobic treatment with a coupling agent such as a silane coupling agent, a titanium coupling agent, a zircoaluminate coupling agent, or silicone oil.

The amount of the filler used depends on its purpose and components, but in most cases is 0.1 to 50% by weight, preferably 0.1 to 10% by weight. There is a possibility that the polymerization may be adversely affected, and the compounding becomes difficult depending on the size of the components contained.

As the coloring agent used in the present invention, inorganic pigments (natural, chromate, ferrocyanide, oxide, chloride, sulfate, silicate, metal powder, etc.) and organic pigments (natural Dye lakes, nitriles, azos, phthalocyanines, condensed polycyclics, basic dye lakes, mordant dyes, vat dyes, etc.), and dyes include water-soluble dyes and oil-soluble dyes.

Specific examples of the inorganic pigments include, for example, natural pigments such as ocher, chromates such as graphite, zinc yellow, barium yellow, chrome orange, molybdenum red and chrome green, and ferrocyan compounds such as navy blue. Oxides such as titanium oxide, titanium yellow, titanium white, red iron oxide, yellow iron oxide, zinc ferrite, zinc white, iron black, cobalt blue, chromium oxide, and spinel green; and sulfides such as cadmium yellow, cadmium orange, and cadmium red And silicates such as calcium silicate and ultramarine, metal powders such as bronze and aluminum, and carbon black.

Specific examples of the organic pigment include, for example, natural lakes such as Madalake, nitroso pigments such as naphthol green and naphthol orange, benzidine yellow G, Hanza yellow G, Hanza yellow 10G, Vulcan orange, lake red R, and lake. Red C, Lake Red D, Watching Red, Brilliantamine 6
B, pyrarozone orange, Bordeaux 10G, soluble azo type such as (Bonmaroon), pyralozone red, para red, toluidine red, ITR red toluidine red (rake red 4R), toluidine maroon, brilliant fist scarred, lake bordeaux 5B, etc. Azo pigments such as inactive azo and condensed azo pigments, phthalocyanine blue, phthalocyanine green, brominated phthalocyanine green, phthalocyanine pigments such as fast sky blue, anthraquino pigments such as sllen blue, perylene pigments such as perylene maroon, perinone Condensed polycyclic pigments such as perinones such as orange, quinacridones such as quinacridone and dimethylquinacridone, dioxazines such as dioxazine violet, isoindoline and quinophthalone, rhodami 6B, lake, rhodamine lake B, basic dye lakes such as malachite green, mordant dye-based pigments such as alizarin lake, Indus Ren blue,
Vat dye pigments such as indigo blue and anthantrone orange, fluorescent pigments, azine pigments (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 the like. Specific examples of oil-soluble dyes include Fast Orange R,
Monoazo dyes such as oil red and oil yellow; anthraquinone dyes such as anthraquinone blue and anthraquinone violet; azine dyes such as nigrosine and indulin; basic, acidic, and metal complex compound dyes; The amount of the colorant used is often 0.1 to 30% by weight, preferably 1 to 30% by weight.
15% by weight.

Examples of the conductive substance of the present invention include various carbon blacks obtained by a channel method, a thermal method, an acetylene method, a furnace method, etc., and γ-Fe203 as a magnetic powder.
, Co-modified FeO _x (eg, CoFe ₂ O ₄ ),
(Mn-Zn) Fe ₂ O ₄ , CrO ₂ , barium ferrite, metallic iron alloy, and the like. The amount of the conductive substance used is often 0.1 to 50% by weight, preferably 1 to 50% by weight.
It is 15% by weight, and as a feature of the present invention, excellent conductivity can be obtained even with a small amount of 10% by weight or less.

The wax used to prevent offset of the polymerized toner of the present invention is preferably a self-emulsifying emulsion wax in consideration of moisture resistance.
Examples of the self-emulsifying emulsion wax include carboxyl group-modified polyolefins,
Polyethylene wax, polypropylene wax, etc., having an olefin unit such as ethylene, propylene, butene-1 or pentene-1 as a skeleton, modified to have a carboxyl group, and at least a part of the carboxyl group being neutralized with ammonia or an amine. It is.

Examples of the charge control agent include electronegative substances such as nigrosine dyes and quaternary ammonium salts as negative charge control agents, and electron charge such as metal salts of monoazo dyes as positive charge control agents. Respirable substances.
The use amount of the wax and the charge control agent is usually 0 to 30% by weight, preferably 1 to 30% by weight.

In the modified polymer particles according to the second invention,
As a combination of the particles A and B, fillers, colorants,
Any combination of conductive material and resin particles is possible.

The condition of the mixing ratio of particles A and B for deforming is 4.0 <(W _A / W _B ) × (ρ _B / ρ _A ).
It is necessary that the ratio is <7.5, and the mixing ratio is particularly 5.0 <(W _A / W _B ) × (ρ _B / ρ _A ) <6.0.
By doing so, deformed polymer particles having a high degree of deformation can be obtained.

The shear flow or stirring flow applied in the production process of the multilayer and irregularly polymerized particles of the present invention can be achieved by using a high-speed homogenizer, a high-pressure homogenizer, a microfluidizer, a Gaulin homogenizer, a Manton-Gaulin homogenizer, or the like. . Also, the flow rate required to generate a shear flow or a stirring flow is
2000-8000 rpm is preferable.

The amount of solids charged in the production process of the multilayer and irregularly shaped polymer particles of the present invention is usually 1 to 30% by weight, preferably 3 to 20% by weight, and the average particle size of the polymerized toner is 1 to 30% by weight. 100 μm, preferably 2 to 20 μm
It is. The polymerization temperature and time may be those known in the art, and generally a temperature of 40 to 100 ° C. for 1 to 50 hours is sufficient. However, the reaction time required for the polymerization system of the present invention is:
In particular, it is characterized in that it tends to be short, and the generation rate of new particles is extremely low even when the amount of the oligomer as a dispersant is increased.

Next, a color image forming apparatus using the above-described polymer particles of the present invention as a developer will be described. In the color image forming apparatus shown in FIG.
1, 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,
Four sets are arranged for four colors of cyan. A transfer material 213 such as paper or an OHP sheet is conveyed on the transfer belt 208 from the direction of the arrow, and a transfer voltage is applied by a transfer device 209 from below the transfer belt 208 at a portion where the transfer material 213 contacts the photoconductor 202. The toner developed on the photoconductor 202 in the process described with reference to FIG. 5 is transferred to the transfer material 213. This is sequentially performed for each color, and the transfer material 2
13 is overlaid with the toner image.

As the transfer device 109, a device that applies a bias voltage to an elastic roller is used. The toner image superimposed on the transfer material 213 is
Heat is applied to the toner by passing between the heating roller 211 and the pressure roller 212 in 10, and the toner is fixed on the image support. Thus, a full-color image is obtained.

FIG. 6 is a sectional view of a contact type non-magnetic one-component developing device 200 used in the color image forming apparatus of FIG. In this example, the blade 110 has a thickness of 0.2
A phosphor bronze plate having a thickness of 80 mm is used, and urethane rubber conforming to JIS-A standard 80 ° is used for a contact portion 109a with the developing roller 109.

FIG. 7 is a conceptual sectional view of the fixing device 210 used in the color image forming apparatus of FIG. The heating roller 211 has a structure in which a silicon rubber layer is formed on a hollow cored bar, 214 is a heater lamp, and 212 is a pressure roller. The pressure roller 212 is formed by forming a silicon rubber layer having a surface coated with a fluorine resin on a cored bar, and is configured to rotate by pressing against a heat roller. When the heating roller 211 is heated, the release agent applying member 215 is also heated, and the silicone oil leaches out,
It is supplied to the heating roller 211. When the heating roller 211 rotates, the excessively supplied silicon oil is scraped off by the cleaning blade 216 and is applied to the surface of the heating roller 211 in a thin film. As the release agent, dimethyl silicone oil having a viscosity of around 300 cs is desirable. Image support 1 between fixing rollers
When 13 passes, a part of the silicon oil adheres to the image support, and the silicon oil is consumed.

Next, the developing method using the conductive toner will be described. The one-component developing method using a conductive toner is roughly classified into two types: a non-magnetic toner type and a magnetic toner type. The schematic diagram of the photoreceptor shown in FIG. 8 schematically shows the principle of a typical charge developing method for a conductive toner. The schematic diagram shown in FIG. 9 schematically shows a developing device using a conductive toner.

The photoreceptor shown in FIG. 8 has a persistent photoconductive layer 502 on an insulating layer 501. In the developing device shown in FIG. 9 using the photosensitive member, when a voltage is applied between the developing roller 601 and the conductive layer of the photosensitive member 602, the photosensitive member 60
The surface of the photoconductor 2 and the conductive toner 603 contacting the surface of the photoconductor 2 are charged, and the toner particles 603 adhere to the surface of the photoconductor 602 by electrostatic attraction between the opposite charge on the back surface of the photoconductor. For example, if the resistance of the toner layer 604 of the conductive toner 603 is relatively low, if a doctor blade 605 for regulating the thickness of the toner layer 604 is grounded, the toner layer from there to the developing section forms a conductive path. , Development becomes possible.

FIG. 10 is a diagram showing the structure of a planar heating element made of a conductive polymer. The planar (film) heating element 701 has a structure in which a conductive material and a polymer obtained by organic polymerization are coated on glass fiber, polyester fiber, Japanese paper, or the like, and electrodes 702 are provided at both ends. Such a heating element 701 is made of an insulating material 7 such as polyester.
03 can be insulated and sealed and processed according to various uses. One example is a heat board shown in FIG. This is a conductive sheet heating element 801 shown in FIG.
Are sandwiched between two insulating materials 802, and a heat insulating material 803 for heat insulation, a cushion material 804 and a surface material 805 for pressure resistance are applied.

Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples of the present invention, but the present invention is not limited thereto. Unless otherwise specified, all quantities are indicated by weight.

First, tests performed in Examples and Comparative Examples will be described below.

The polymerized toner produced by the method of the present invention is provided with a one-component contact developing device shown in FIG. 6 and a heat roller heat fixing device (nip width 7.5 mm) having a surface temperature of 128 ° C. shown in FIG. Used as a developer for a printer having the blade cleaning device shown in FIG. 5 at a process speed of 105 mm / sec.
And a 20 mm square solid black batch image was output.
Further, it was mixed with a ferrite carrier having an average particle size of about 60 μm at a weight ratio of 100: 4, and the surface temperature of the two-component developing device was 128
An image output was performed in the same manner as described above, using a heat roller heat fixing device (nip width 7.5 mm) at ℃ and a blade cleaning device, and using as a developer toner of a printer with a process speed of 65 mm / sec. Then, the image density of the solid black batch was measured with a MACBETHR918 reflection thermometer, and evaluated based on the following criteria.

1. Low-temperature fixability test Measurement was performed by rubbing the black solid batch toner fixing unit output by the above one-component or two-component printer with a cloth tester under the condition of 300 cloths, and measuring the image density before and after the test with a reflection densitometer. And the ratio was evaluated. With both printers, the ratio of the image density before and after the test was 90% or more, ○, and less than 90%, X. Further, the fixing rate here is the ratio of the image density.

2. Friction Resistance Test Adhesion in Developing Unit (Number of Running Units) SEM observation of the surface of the developing roller and the charging blade was performed, and it was determined whether or not toner adhesion occurred on the charging blade and the developing roller. If no sticking was observed in the developing device after 30,000 sheets were printed, it was marked as "A", and if sticking was seen and the image uniformity was deteriorated, it was marked as "D".

3. Cleanability Test After printing a predetermined number of sheets at a printing rate of 6%, the image was judged by the presence or absence of a character memory or a streak-like defective image on the image. After printing 30,000 sheets, the determination was made based on the presence or absence of a character memory or a streak-like defective image on the image.場合 indicates that no printing occurred on 30,000 sheets, and x indicates that printing occurred.

4. Conductivity test A sheet heating element in which conductive plastic particles were applied to glass fiber was fixed to a clip, and the resistance (Ω) was determined by a constant current method in which a constant amount of electricity was supplied. When the resistance was 150 Ω or less, the evaluation was ○.

5. Moisture resistance test (1) Fog test (moisture resistance test of polymerized toner)
Was mixed at a weight ratio of 100: 4 and used as a developer for the printer shown in FIG. 5 at a process speed of 65 mm / sec. This printer is equipped with a two-component developing device, a heat roller heat fixing device having a surface temperature of 128 ° C. (nip width: 7.5 mm), and a blade cleaning device.

The polymerized toner thus obtained was dried at 45 ° C. for 50 hours, and an image was output in an atmosphere of normal temperature and normal humidity at a temperature of 20 ° C. and a humidity of 50%. Lightness of tape taped (%)
Was measured. After that, after being placed in a high-temperature and high-humidity atmosphere at a temperature of 30 ° C. and a humidity of 85%, the lightness (%) of the taped toner image on the first photoconductor 12 hours later was measured and compared with the above lightness. And those with a difference of 5% or more
Use a small one for ○ (lightness is measured using a colorimeter Minolta CR
Measured by -10. ).

(2) Moisture content (moisture resistance test of conductive plastic particles for sheet heating element) The final particles were subjected to a normal temperature and normal humidity atmosphere at a temperature of 20 ° C and a humidity of 50%.
The sample was placed in a high-temperature, high-humidity atmosphere at a temperature of 30 ° C. and a humidity of 85% for 12 hours, and then the moisture content was measured. The moisture content was measured by the Karl Fischer method at a sample heating temperature of 200 ° C. and a required time of 15 minutes.

6. Layer Formability and Deformation Test The layer formability was evaluated by TEM (H-60)
0, HITACHI) observation. If the layer was formed, it was evaluated as ○, and if not, it was evaluated as ×. In addition, the deformability test was performed using SEM (ABT-32, TBT) of the polymer particles after drying.
OPCON). × for a true sphere,
The others were marked with ○.

7. Size test of polymerized particles Particle counter (CAPA-700, HORI
BA), the volume average particle size was measured. If the value was a submicron size, x was given, and the other values were given as o. [Example 1-1] 1. Synthesis of resin particles Styrene: 16 parts n-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion exchange water: 79 parts The above polymerizable monomer is dissolved in an aqueous solution obtained by dissolving the above ammonium persulfate in the above ion exchange water. The mixture was 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, and the average particle size was 0.8 μm.
m of resin particles were obtained.

2. Distributed feldspar powder filler _{(K 2 O · Al 2 O} 3 · SiO 2): 15 parts of the cationic oligomer 4 parts Ion exchange water: 100 parts The above ingredients in a ball mill (HD pot mill typeA-
3 (manufactured by Nicker Co., Ltd.) for 10 hours to obtain a filler dispersion having an average particle size of 0.03 μm. The cationic oligomer used above had a weight average molecular weight of 5,000.
And the structural formula is CH ₂ ＣＲCR ₁ COO (CH ₂ ) _n -NHR
₂ R ₃ (n is an integer of 1 to 10, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 6 carbon atoms). The particle diameter difference filler and the resin particles ^{_{(R A + R B) 2}} / R B 2 =
765> 121.

3. Synthesis of Multilayer Polymer Particles Resin particles: 12 parts Filler dispersion: 5 parts Ion-exchanged water: 430 parts The above was stirred and mixed with a stirring rod to obtain a dispersion. Next, 40 parts of styrene in which 0.3 part of azobisisobutylnitrile was dissolved was added to the dispersion, and the dispersion was added with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
The mixture was stirred at 000 rpm for 10 minutes, and reacted 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 polymer particles having an average particle size of 8.0 μm.

4. Test of Multilayer Polymerized Particles As a layer formation confirmation test, TEM observation revealed that a layer in which fillers were uniformly dispersed was formed on the particle surface as shown in FIG. [Example 1-2] The same procedure as in Example 1-1 was carried out except that a step of adding a colorant to the resin particles shown below was added, and the composition and composition of the polymerized monomer to be added were changed as follows. A polymerized toner having an average particle size of 9.0 μm having a filler layer on the surface was obtained.

1. Synthesis of Colorant-Containing Resin Particles Carbon black: 2 parts Anionic oligomer: 10 parts Styrene: 16 parts N-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion-exchanged water: 79 parts Dissolve,
The polymerizable monomer was added, and the mixture was 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 polymer particles having an average particle diameter of 0.8 μm. The above oligomer has a weight average molecular weight of 7000 and a structural formula (n: an integer of 1 to 10, R1, R2, R3:
An alkyl group having 1 to 6 carbon atoms) is CH2 = CR1COO
An anionic oligomer of (CH2) nCH2 = CH-ＣＨ-OSO3NH4 was used.

2. Synthesis of Polymerized Toner Having Filler Layer Colorant-containing resin particles: 12 parts Filler dispersion: 5 parts Ion-exchanged water: 430 parts The above were mixed with a stirring rod to obtain a dispersion. Next, 32 parts of styrene obtained by dissolving 0.3 parts of azobisisobutylnitrile and 8 parts of n-butyl acrylate were added to the dispersion, and a homogenizer (TK AUTO, manufactured by Tokushu Kika Kogyo Co., Ltd.) was added.
Stir at 5000 rpm for 10 minutes with a homomixer.
The reaction was carried out in a 4 liter four-necked flask at a stirring speed of 80 rpm, a polymerization temperature of 80 ° C. and a polymerization time of 3 hours.
A polymerized toner of 0 μm was obtained. T as a layer formation confirmation test
EM observation confirmed that a layer in which the filler was uniformly dispersed was formed on the particle surface as shown in FIG.

3. Test of Polymerized Toner 1.0% by weight of hydrophobic silica was added to the polymerized toner having a filler layer obtained in 2 and mixed with a Henschel mixer.
The final toner was obtained. The toner was image-outputted at the set temperature of the heat roller of 128 ° C. using the above-described non-magnetic one-component printer and two-component printer. When the image density of the solid black patch was measured with a MACBETHR918 reflection densitometer, a high density of 1.42 was obtained. As a test of low-temperature fixability, the fixability of a solid black image was measured, and a good fixation rate of 90% was obtained.

After the development of 30,000 sheets as a test of friction resistance, SEM observation of the surface of the developing roller and the charging blade revealed no toner adhesion on the charging blade and the developing roller. The softening point of the toner was measured by a flow tester (CFT-500, manufactured by Shimadzu Corporation) and found to be 120 degrees. In addition, good results were obtained in the moisture resistance fogging test. [Example 1-3] In Example 1-2, 5 parts of feldspar powder was used as 8 parts of hematite (Fe203), and the average particle size was 0.07.
A micron dispersion was obtained. Therefore, difference in particle diameter of the filler and the resin particles ^{_{(R A + R B) 2}} / R B 2 = 155> 121
It is. Other conditions were the same, and the average particle size was 9.5 μm.
Thus, a polymerized toner having a m filler layer was obtained. Good results were obtained in the low-temperature fixability test, the friction resistance test, and the moisture resistance test. Examples 1-4, 5, 6 Examples 1-2 except that phthalocyanine blue, benzidine yellow and permanent rhodamine were used instead of carbon black.
Similarly, a polymerized toner having a filler layer having a thickness of 9.0 μm, 8.5 μm, and 9.5 μm was obtained. The judgment of the test result was the same as in Example 1-2. Further, it was confirmed that the color toner also exhibited excellent low-temperature fixability, friction resistance, and moisture resistance. Comparative Example 1-1 The procedure of Example 1-1 was repeated except that the oligomer used for filler dispersion was changed to sodium dodecylbenzenesulfonate. Did not. [Comparative Example 1-2] as follows, the particle diameter of the resin particles is 0.3 microns, as difference in particle diameter of the filler and the resin particles is ^{_{(R A + R B) 2}} / R B 2 = 121 Except that the polymerization was carried out in the same manner as in Example 1-1, the average particle size was submicron, and micron-sized particles could not be obtained.

Synthesis of Resin Particles Styrene: 16 parts n-butyl acrylate: 4 parts Acrylic acid: 1 part Ammonium persulfate: 1 part Ion-exchanged water: 79 parts Aqueous solution obtained by dissolving the above ammonium persulfate in the above ion-exchanged water The above polymerizable monomer was added thereto, and the mixture was 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, and the average particle size was 0.3 μm.
m of resin particles were obtained. [Comparative Example 1-3] Polymerization was carried out in the same manner as in Example 1-1, except that the terminal group of the cationic oligomer in the filler dispersion was a quaternary ammonium salt, and the average particle size was 8.0.
Micron polymer particles were obtained, but when a layer formation test was performed, no layer structure was observed by TEM. Further, in the moisture resistance test, it was found that the moisture absorption rate at high temperature and high humidity increased and the moisture resistance was poor. [Comparative Example 1-4] Styrene monomer 80 parts by weight butyl acrylate 5 parts by weight Styrene-acrylate latex (softening point 120 degrees) 5 parts by weight Sodium dodecylbenzenesulfonate 1 part by weight Benzoyl veroxide 1 part by weight Carbon black 7 parts by weight Part Quaternary ammonium salt-based negative charge control agent (CCA) 1 part by weight A ball mill (HD pot mill type A-
3 (manufactured by Nicker Co., Ltd.) for 40 hours. K. The mixture was stirred with an AUTO homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 15 minutes at a rotation speed of 12,000 rpm, transferred to a 2-liter four-necked flask containing ion-exchanged water, and further stirred at 1000 rpm for 2 hours, and then the rotation speed was changed to 250 rpm.
m, the temperature was set to 70 ° C., and polymerization was carried out for 8 hours. The obtained polymer particles had a volume average particle size of 7.0 μm. 1.0 wt% of hydrophobic silica was added to this toner and mixed with a Henschel mixer to obtain a final core-shell type capsule toner.

When a cross-sectional view of this toner was observed by TEM observation, a high molecular weight core layer was observed. When this toner was subjected to image output at a heat roller setting temperature of 118 ° C. using the above-described non-magnetic one-component printer and two-component printer, an image density of 1.20 of a solid black batch was obtained.
In the low-temperature fixing property test, the fixing property was measured and found to be 40%. After 30,000 sheets were developed as a friction resistance test, SEM observation of the surface of the developing roller and the charging blade was performed. As a result, no toner was fixed on the charging blade and the developing roller. The softening point of the toner was measured using a flow tester (CFT-50, manufactured by Shimadzu Corporation).
It was 135 degreeC as measured by 0). In the moisture resistance test, it was found that the fog was 10% and the moisture resistance was poor. [Example 2-1] 1. Synthesis of anionic resin particles Styrene: 16 parts n-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion-exchanged water: 79 parts The polymerization was carried out 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, and the average particle size was 0.8 μm.
m polymer particles were obtained.

[0096] 2. Synthesis of cationic resin particles Styrene: 20 parts Cationic oligomer: 4 parts AIBN · 2HCl (isobutylamide hydrochloric acid): 1 part Ion exchange water: 75 parts AIBN · 2HCl (isobutylamide hydrochloric acid) The above polymerizable monomer was added to an aqueous solution obtained by dissolving in ion-exchanged water, and reacted in a 1-liter four-neck flask at a stirring speed of 250 rpm, a polymerization temperature of 70 ° C. and a polymerization time of 8 hours, and the average particle diameter was determined. 0.03 μm resin particles were obtained.

The cationic oligomer used above has a weight average molecular weight of 5000 and a structural formula of CH ₂ CR ₁ COO.
(CH ₂ ) _n -NHR ₂ R ₃ (where n is an integer of 1 to 10, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 6 carbon atoms).

Here, the difference in particle size between the anionic and cationic resin particles is (R _A + R _B ) ² / R _B ² = 765> 121
It is.

3. Synthesis of Deformed Polymer Particles Anionic resin particles: 27 parts Cationic resin particles: 5 parts Ion-exchanged water: 430 parts The above were mixed with a stirring rod to obtain a dispersion. 20 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile was added to this dispersion, and 1 part was added at 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
The mixture was stirred for 0 minutes, and reacted 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 polymer particles having an average particle size of 7.5 μm. As shown in FIG. 2A, it was confirmed by SEM observation as a shape confirmation test that the polymer particles were deformed and had a depression on the particle surface. [Example 2-2] Polymer particles having an average particle size of 8.0 µm were obtained in the same manner as in Example 2-1 except that the synthesis of the last modified polymer particles was performed as follows. SEM observation as a shape confirmation test confirmed that the polymer particles were deformed and had a plurality of depressions on the particle surface, as shown in FIG. 2B.

Synthesis of Deformed Polymer Particles Anionic resin particles: 22 parts Cationic resin particles: 5 parts Ion-exchanged water: 430 parts The above were mixed with a stirring rod to obtain a dispersion. Next, 20 parts of styrene obtained by dissolving 0.3 parts of azobisisobutylnitrile was added to this dispersion, and the mixture was subjected to 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
and a stirring speed of 80 rpm, a polymerization temperature of 80 ° C. and a polymerization time of 3 in a 1 liter four-necked flask.
The reaction took place over time. [Example 2-3] A modified polymer toner was synthesized in the same manner as in Example 2-1 except that carbon black was dispersed as a coloring agent in place of the synthesis of the cationic resin as follows. Polymer particles having an average particle size of 8.0 μm were obtained. By SEM observation as a shape confirmation test, as shown in FIG. 2A, it was confirmed that the polymer particles were deformed and had a depression on the particle surface.

1. Dispersion of carbon black Carbon black: 15 parts Cationic oligomer: 4 parts Ion-exchanged water: 100 parts The above raw materials were ball milled (HD pot mill type A-
3 (manufactured by Nicker Co., Ltd.) for 10 hours to obtain a carbon black dispersion having an average particle size of 0.03 μm.
The cationic oligomer used above has a weight average molecular weight of 5000 and a structural formula of CH ₂ ＣＲCR ₁ COO (CH ₂ ) _n.
—NHR ₂ R ₃ (wherein, n is an integer of 1 to 10, R ₁ , R
₂ , R ₃ is a weak base having 1 to 6 carbon atoms). The difference in particle size between carbon black and resin particles is (R _A + R
^{_{B) 2 / R B 2 =}} 765> is 121.

2. Synthesis of Deformed Polymerized Toner Anionic resin particles: 15 parts Carbon black dispersion: 5 parts Ion-exchanged water: 430 parts The above were mixed with a stirring bar to obtain a dispersion. Next, 20 parts of styrene obtained by dissolving 0.3 parts of azobisisobutylnitrile was added to this dispersion, and the mixture was subjected to 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
Then, the mixture was stirred at a stirring speed of 80 rpm, a polymerization temperature of 80 ° C. and a polymerization time of 3 hours in a 1-liter four-necked flask to obtain a polymerized toner having an average particle size of 8.5 μm.

According to SEM observation as a shape confirmation test,
As shown in FIG. 2A, it was confirmed that the polymerized toner had a deformed portion having a depression on the particle surface. In the cleaning test, no character memory was generated even after printing 30,000 sheets. In addition, in the moisture resistance fogging test, 5%
The following were good results. [Example 2-4] In the synthesis of anionic resin particles,
Examples 2-3 except that one part of acrylic acid was added
In the same manner as in the above, a dispersion having an average particle size of 0.5 μm was obtained. Therefore, the difference in particle size between the two resin particles is (R _A + R _B )
² / R _B ² = 312> is 121. Other conditions were the same as in Example 2-3 to obtain a modified polymer toner having an average particle size of 9.0 μm as shown in FIG. This modified polymer toner also showed good results in the tests of cleaning properties and moisture resistance. [Examples 2-5, 6, 7] Examples 2-3 except that phthalocyanine blue, benzidine yellow, and permanent rhodamine were used instead of carbon black.
In the same manner as described above, modified polymer toners of 9.5 μm, 8.5 μm, and 9.0 μm as shown in FIG. 2A were obtained. The judgment of the test result was the same as in Example 2-3. It was confirmed that the toner has excellent cleaning properties and moisture resistance as a color toner. [Comparative Example 2-1] Polymerization was carried out in the same manner as in Example 2-1 except that the anionic resin was used instead of the cationic resin as described below. Was not obtained.

Synthesis of anionic resin particles Styrene: 16 parts n-butyl acrylate: 4 parts Sodium dodecylbenzenesulfonate: 1 part Ammonium persulfate: 1 part Ion exchange water: 79 parts The above ammonium persulfate is dissolved in the above ion exchange water The polymerizable monomer was added to the aqueous solution obtained in the above, and the mixture was stirred in a 1-liter four-necked flask at a stirring speed of 250 rpm and a polymerization temperature of 7 mL.
The reaction was carried out at 0 ° C. for a polymerization time of 8 hours, and the average particle size was 0.03 μm.
m polymer particles were obtained. [Comparative Example 2-2] The particle size of the resin particles was set to 0.
3 μm, and the difference in particle size between the two resin particles is (R _A + R
_B) except that was set to be ² / R _B ² = 121, was polymerized in the same manner as in Example 2-1, the average particle size becomes submicron, micron sized particles were not obtained.

Synthesis of Resin Particles Styrene: 16 parts N-butyl acrylate: 4 parts Acrylic acid: 1 part Ammonium persulfate: 1 part Ion exchange water: 79 parts Aqueous solution obtained by dissolving the above ammonium persulfate in the above ion exchange water The above polymerizable monomer was added thereto 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, and the average particle size was 0.3 μm.
m polymer particles were obtained. [Comparative Examples 2-3, 4] An average particle diameter of 7 was obtained in the same manner as in Example 2-3 except that the following spherical polymerized toner was synthesized instead of the last modified polymerized toner. .
A polymerized toner of 5 μm was obtained.

Synthesis of Spherical Polymerized Toner Anionic resin particles: 16 parts, 15 parts Carbon black dispersion: 5 parts, 8 parts Ion-exchanged water: 430 parts The above were mixed with a stirring rod to obtain a dispersion. Next, 20 parts of styrene obtained by dissolving 0.3 parts of azobisisobutylnitrile was added to this dispersion, and the mixture was subjected to 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
Then, the mixture was stirred 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 a polymerized toner having an average particle size of 7.5 and 8.0 μm. SEM observation as a shape confirmation test confirmed that both were spherical polymerized toners as shown in FIG. 2 (c). In the cleaning test, a character memory was generated after printing 1,000 sheets. In addition, in the moisture resistance fogging test, it was 5% or less, which was a good result. [Comparative Example 2-5] Polymerized particles having an average particle size of 8.0 µm by polymerization in the same manner as in Example 2-3, except that the terminal group of the cationic oligomer in the carbon black dispersion was a quaternary ammonium salt. However, according to SEM as a shape test, it was observed that the toner was a modified polymer toner as shown in FIG. In addition, although the cleaning property was good, it was found in the moisture resistance test that the moisture absorption rate at high temperature and high humidity increased and the moisture resistance was poor. [Comparative Example 2-6] Styrene monomer 60 parts Butyl acrylate 15 parts Acrylic acid 2 parts Sodium dodecylbenzenesulfonate 1 part Benzoyl veroxide 1 part 20% anionic resin emulsion 30 parts 10% cationic carbon black dispersion 40 parts More than 150 parts of water was dispersed by a ball mill and a Nanomizer to obtain a mixed solution. The pH of the mixed solution was adjusted to about 8.0 with sodium hydrogen phosphate, and the stirring speed was set to 450 rpm.
The mixture was polymerized at a reaction temperature of 90 ° C. for 8 hours to obtain primary particles having a volume average particle size of 5 μm.

Next, the temperature was lowered to 50 to 60 ° C., the primary particles were aggregated at a stirring speed of 200 rpm, and secondary particles having a volume average particle size of 9.5 μm were formed. Aging was performed at 98 ° C. for 4 hours and 8 hours to obtain amorphous aggregated particles having a solid content of about 30%. These are each filtered and washed, and vacuum dried at 45 ° C. for 1 hour.
The operation was performed for 0 hour to obtain a final irregular-shaped toner. The average particle size of this irregular toner was 8.0 μm. In addition, although the cleaning property was good, a character memory was generated after printing 2000 sheets in the friction resistance test. [Example 3-1] 1. Synthesis of Colorant-Containing Resin Particles Carbon black: 2 parts Anionic oligomer: 10 parts Styrene: 16 parts n-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion-exchanged water: 79 parts The polymerizable monomer was added to the aqueous solution obtained by dissolution, and the mixture was stirred in a 1-liter four-necked flask at a stirring speed of 250 rpm and a polymerization temperature of 7 mL.
The reaction was carried out at 0 ° C. for a polymerization time of 8 hours.
Resin particles were obtained. The anionic oligomer has a weight average molecular weight of 7,000, and its structural formula is CH ₂ C
R ₁ COO (CH ₂ ) _n CH ₂ ＣＨCH- ◎ -OSO ₃ N
H ₄ (n: an integer of 1 to 10, R ₁ : an alkyl group having 1 to 6 carbon atoms).

2. Filler dispersion Feldspar powder: 15 parts Cationic oligomer: 4 parts Ion-exchanged water: 100 parts The above raw materials were ball milled (HD pot mill type A-
3 (manufactured by Nicker Co., Ltd.) for 10 hours to obtain a carbon black dispersion having an average particle size of 0.03 μm.
The cationic oligomer used above has a weight average molecular weight of 5000 and a structural formula of CH ₂ ＣＲCR ₁ COO (CH ₂ ).
_{n -NHR 2 R 3 (n:} 1~10 integer, R _1, R _2,
R ₃ : an alkyl group having 1 to 6 carbon atoms). The particle diameter difference filler and the resin particles, (R _A + R _B)
² / R _B ² = 765> 121.

3. Synthesis of Deformed / Multilayer Polymerized Toner Colorant-containing resin particles: 12 parts Filler dispersion: 5 parts Ion-exchanged water: 430 parts The above were mixed with a stirring rod to obtain a dispersion. Next, 12 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile and 3 parts of n-butyl acrylate were added to the dispersion, and a homogenizer (TK AUTO, manufactured by Tokushu Kika Kogyo Co., Ltd.) was added.
Stir at 5000 rpm for 10 minutes with a homomixer.
The reaction was carried out in a 4-liter four-neck flask at a stirring speed of 80 rpm, a polymerization temperature of 80 ° C. and a polymerization time of 3 hours to obtain polymer particles having an average particle size of 8.0 μm.

According to SEM observation as a layer formation confirmation test, as shown in FIG. 3, it was confirmed that a layer in which the filler was uniformly dispersed was formed on the particle surface, and that the toner was a modified polymer toner by SEM observation. Was. 1.0 wt% of hydrophobic silica was added to this toner and mixed with a Henschel mixer to obtain a final toner. An image was output from the toner using the above-described non-magnetic one-component printer and two-component printer at a set temperature of the heat roller of 128 degrees. When the image density of the solid black batch was measured, a high density of 1.45 was obtained.

As a test for the low-temperature fixability, the fixability was measured, and a good fixation rate of 92% was obtained. After the development of 30,000 sheets as a friction resistance test, SEM observation of the surface of the developing roller and the charging blade was performed. As a result, no toner was fixed on the charging blade and the developing roller. The softening point of the toner was measured by a flow tester (CFT-500, manufactured by Shimadzu Corporation) and found to be 120 degrees. Further, in the cleaning test, no character memory was generated even after 30,000 sheets were output, which was good. According to the moisture resistance test, good results were obtained in the fogging test. [Example 3-2] 5 parts of feldspar powder was converted to alumina (Al ₂ O ₃ )
Except having set it as 7 parts, like Example 3-1
A dispersion having an average particle size of 0.07 microns was obtained. Therefore, difference in particle diameter of the filler and the resin particles ^{_{(R A + R B) 2}} / R B 2
= 155> 121. Other conditions are the same as those in Example 3
In the same manner as in Example 1, a modified polymer toner having a filler layer having an average particle size of 9.5 μm was obtained. Both the low-temperature fixing property test, the friction resistance test, the cleaning property, and the moisture resistance test were performed, and the results were good. [Examples 3-3, 4, 5] Example 3-1 except that phthalocyanine blue, benzidine yellow and permanent rhodamine were used instead of carbon black.
In the same manner as described above, a modified polymer toner having a filler layer of 7.0 μm, 7.5 μm, and 8.0 μm was obtained. The result of each test was the same as in Example 3-1. As a color toner, low-temperature fixability test, friction resistance test, cleaning property, and moisture resistance test were all good. [Comparative Example 3-1] The average particle diameter was the same as in Example 3-1 except that the following spherical multi-layer polymerized toner was synthesized instead of the final modified multi-layer polymerized toner. A polymerized toner of 7.0 μm was obtained.

Synthesis of Spherical / Multilayer Polymerized Toner Colorant-containing resin particles: 20 parts Filler dispersion: 7 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 0.3 parts of azobisisobutylnitrile was dissolved in this dispersion, and a homogenizer (TK AUTO, manufactured by Tokushu Kika Kogyo Co., Ltd.) was used.
Stir at 5000 rpm for 10 minutes with a homomixer.
The reaction was carried out in a 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 a polymerized toner having an average particle size of 7.5 μm. T as a layer formation test
When the cross section of the particles was observed by EM, a layer in which the filler was uniformly dispersed on the particle surface could be confirmed.

Further, when observed by SEM as a shape confirmation test, it was confirmed that the toner was a spherical polymerized toner. In the cleaning test, a character memory was generated after printing 1,000 sheets. In the low-temperature fixing property test, the fixing rate was 9%.
It was as good as 3%, and there was no sticking in the friction resistance test. [Comparative Example 3-2] After the polymerizable monomer was swollen into particles by stirring at a stirring speed of 80 rpm for 10 hours instead of 5000 rpm of a homogenizer, acrylic acid was added to make the PH acidic, and it took another 10 hours. Polymerized toner having an average particle size of 8.0 microns was obtained in the same manner as in Example 3-1 except that the granulation was performed while stirring.

According to SEM observation as a shape confirmation test,
It was confirmed that the toner was a grape-like polymerized toner. In the cleaning test, no character memory was generated after printing 30,000 sheets. In the low-temperature fixability test, the fixation rate was 90%, which was good. However, in the friction resistance test, sticking and crushed particles were generated. In the moisture resistance fog test, good results were obtained at 5% or less. [Comparative Example 3-3] When a cleaning test was performed on the core-shell type capsule toner obtained in the same manner as in Comparative Example 1-4 of the first invention, a character memory was generated after printing 1,000 sheets. Other tests performed well. [Comparative Examples 3-4 and 5] In the synthesis of the last modified / multi-layer polymerized toner, the average particle diameter was 7.0 in the same manner as in Example 3-1 except that the synthesis was performed according to the following formulation. 5,
An 8.5 μm polymerized toner was obtained.

Synthesis of Deformed / Multilayer Polymerized Toner Anionic resin particles: 16 parts, 15 parts Carbon black dispersion: 5 parts, 8 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Was. Next, 20 parts of styrene in which 0.3 part of azobisisobutylnitrile was dissolved was added to the dispersion, and the mixture was subjected to 5000 r with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
The mixture was stirred for 10 minutes at pm, and reacted 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 a polymerized toner having an average particle size of 7.5 μm and 8.0 μm.

By SEM observation as a shape confirmation test,
In both cases, it was confirmed that the toner was a modified polymer toner as shown in FIG. However, in the cleaning test,
Character memory occurred after printing 2000 sheets. Further, in the moisture resistance fogging test, a good result of 5% or less was obtained. [Comparative Example 3-6] As described below, the particle diameter of the resin particles was set to 0.3 μm, and the particle diameter difference between the two resin particles was set to (R _A
+ R _B) except that the ² / R _B ² = 121 to become such, was polymerized in the same manner as in Example 3-1, the average particle size becomes submicron, no micron-sized particles are obtained Was.

Synthesis of Resin Particles Styrene: 16 parts N-butyl acrylate: 4 parts Acrylic acid: 1 part Ammonium persulfate: 1 part Ion exchange water: 79 parts Aqueous solution obtained by dissolving the above ammonium persulfate in the above ion exchange water The above polymerizable monomer was added thereto 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, and the average particle size was 0.3 μm.
m polymer particles were obtained. [Comparative Example 3-7] Polymerization was carried out in the same manner as in Example 3-1 except that sodium dodecylbenzenesulfonate was used as the oligomer used for filler dispersion. Was not obtained. [Example 4-1] 1. Synthesis of resin particles Styrene: 16 parts N-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion exchange water: 79 parts The above polymerizable monomer is dissolved in an aqueous solution obtained by dissolving the above ammonium persulfate in the above ion exchange water. And stirred in a 1 liter four-necked flask at a stirring speed of 250 rpm and a polymerization temperature of 7
The reaction was carried out at 0 ° C. for a polymerization time of 8 hours.
Resin particles were obtained.

[0118] 2. Dispersion of magnetic powder Magnetic powder (Fe ₂ O ₃ ): 15 parts Cationic oligomer: 4 parts Ion-exchanged water: 100 parts The above raw materials were ball milled (HD pot mill type A-
3 (manufactured by Nicker Co., Ltd.) for 10 hours to obtain a magnetic powder dispersion having an average particle size of 0.03 μm. The cationic oligomer used above has a weight average molecular weight of 5000 and a structural formula of CH ₂ ＝ CR ₁ COO (CH ₂ ) _n -NHR ₂
R _{3 is} a weak base. The difference in particle size between the magnetic powder and the resin particles is (R
Is ^{_{A + R B) 2 / R}} B 2 = 765> 121.

3. Synthesis of Conductive Polymerized Toner Resin particles: 20 parts Magnetic powder dispersion: 5 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 9.6 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile and 2.4 parts of n-butyl acrylate were dissolved in this dispersion.
And a homogenizer (TKA manufactured by Tokushu Kika Kogyo Co., Ltd.)
Stir at 5000 rpm for 10 minutes with a UTO homomixer, and stir at 80 rpm in a 1 liter four-necked flask.
m, a polymerization temperature of 80 ° C. and a polymerization time of 3 hours to obtain polymer particles having an average particle size of 7.5 μm.

TEM as conductive layer and shape confirmation test
Observation confirmed that the polymer particles were spherical polymer particles in which the conductive material was uniformly localized on the particle surface, as shown in FIG. 4 (c). 1.0 wt% of hydrophobic silica was added to this toner and mixed with a Henschel mixer to obtain a final toner. Using this toner, an image was output at a set temperature of the heat roller of 128 degrees by a developing method as shown in FIG. When the image density of the solid black batch was measured, all were high. When the fixing property was measured as a low-temperature fixing property test, the fixing rate was 90% in all cases.
That is all, and good results were obtained. Example 4-2 Polymer particles having an average particle size of 7.0 μm were obtained in the same manner as in Example 4-1 except that the synthesis of the last conductive toner was performed as follows. By TEM observation as a shape confirmation test, as shown in FIG. 4 (b), a deformed polymer particle having a plurality of depressions on the particle surface and a conductive substance uniformly localized on the particle surface was obtained. It was confirmed that there was. 1.0 wt% of hydrophobic silica was added to this toner and mixed with a Henschel mixer to obtain a final toner.

Using this toner, an image was output at a set temperature of the heat roller of 128 degrees by a developing method as shown in FIG. When the image density of the solid black batch was measured, all were high. In addition, when the fixing property was measured as a low-temperature fixing property test, the fixing rate was 90% or more in all cases, and good results were obtained.

Synthesis of Conductive Toner Resin particles: 20 parts Carbon black dispersion: 6 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 10 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile and 2.5 parts of n-butyl acrylate were added to the dispersion.
And a homogenizer (TKA manufactured by Tokushu Kika Kogyo Co., Ltd.)
Stir at 5000 rpm for 10 minutes with a UTO homomixer, and stir at 80 rpm in a 1 liter four-necked flask.
m, a polymerization temperature of 80 ° C., and a polymerization time of 3 hours. Example 4-3 Polymer particles having an average particle size of 9.0 μm were obtained in the same manner as in Example 4-1 except that the synthesis of the last conductive toner was performed as follows. As a result of TEM observation as a shape confirmation test, as shown in FIG. 4 (a), deformed polymer particles having a plurality of depressions on the particle surface and a conductive substance uniformly localized on the particle surface. Was confirmed. 1.0 wt% of hydrophobic silica is added to this toner.
And mixed with a Henschel mixer to obtain the final toner.

Using this toner, an image was output at a set temperature of the heat roller of 128 degrees by the developing method shown in FIG. When the image density of the solid black batch was measured, all were high. Also, as a test for low-temperature fixability,
When the fixing property was measured, the fixing rate was 90% in all cases.
That is all, and good results were obtained.

Synthesis of conductive toner Resin particles: 20 parts Carbon black dispersion: 8 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 10 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile and 2.5 parts of n-butyl acrylate were added to the dispersion.
And a homogenizer (TKA manufactured by Tokushu Kika Kogyo Co., Ltd.)
Stir at 5000 rpm for 10 minutes with a UTO homomixer, and stir at 80 rpm in a 1 liter four-necked flask.
m, a polymerization temperature of 80 ° C., and a polymerization time of 3 hours. Example 4-4 Resin particles having an average particle size of 0.5 μm were obtained in the same manner as in Example 4-1 except that one part of acrylic acid was added in the synthesis of anionic resin particles. Therefore, the particle size of the resin particles and the carbon black is (R
Is ^{_{A + R B) 2 / R}} B 2 = 312> 121. Other conditions were the same as in Example 4-1, and the average particle size was 9.0.
A μm conductive toner was obtained. When a test was conducted on this conductive toner, the resistance was low, and the conductivity and the moisture resistance were good, similarly to the results obtained in Example 4-1. [Comparative Example 4-1] Styrene: 60 parts n-butyl acrylate: 15 parts Magnetic powder: 25 parts These were stirred at a stirring speed of 2 in a 1-liter four-necked flask.
The reaction was carried out at 50 rpm, a polymerization temperature of 70 ° C. and a polymerization time of 8 hours, and then the mixture was sliced. When the resistance of the obtained sample was measured by a constant current method, it showed a low value of 110Ω, and good conductivity was confirmed. However, in the low-temperature fixability test, since the carbon content was high, the fixation rate was 50%.
%. No conductive layer was observed by TEM observation. [Comparative Examples 4-2 and 3] Example 4 was repeated except that styrene was used in 4 parts and 13 parts in the synthesis of the conductive toner.
Polymer particles were obtained in the same manner as in Example 1. However, the polymer particles containing 4 parts of styrene lacked the amount of the reactive monomer, and the magnetic powder was not fixed on the surface. In the case of using 13 parts of styrene, the resistance value was as high as 400 ohm in the conductivity test, and the conductivity was poor. [Comparative Example 4-4] The particle diameter of the resin particles was set to 0.
3 μm, and the particle size difference between the resin particles and the magnetic powder is (R _A +
Polymerization was performed in the same manner as in Example 4-1 except that R _B ) ² / R _B ² = 121, and the average particle size of the obtained polymer particles was submicron, and micron-size polymerization was performed. No particles were obtained.

Synthesis of Resin Particles Styrene: 16 parts n-butyl acrylate: 4 parts Acrylic acid: 1 part Ammonium persulfate: 1 part Ion exchange water: 79 parts The above ammonium persulfate was dissolved in the above ion exchange water,
The 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 polymer particles having an average particle diameter of 0.3 μm. [Comparative Example 4-5] Polymerization was carried out in the same manner as in Example 4-1 except that sodium dodecylbenzenesulfonate was used as the oligomer used for dispersing the magnetic powder. The average particle size of the obtained polymer particles was obtained. Was submicron, and micron-sized polymer particles could not be obtained. [Example 5-1] 1. Synthesis of resin particles Styrene: 16 parts N-butyl acrylate: 4 parts Ammonium persulfate: 1 part Ion exchange water: 79 parts The above ammonium persulfate is dissolved in the above ion exchange 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 polymer particles having an average particle diameter of 0.8 μm.

2. Dispersion of carbon black Carbon black: 15 parts Cationic oligomer: 4 parts Ion-exchanged water: 100 parts The above raw materials were ball milled (HD pot mill type A-
3 (manufactured by Nicker Co., Ltd.) for 10 hours to obtain a carbon black dispersion having an average particle size of 0.03 μm.
The cationic oligomer used above has a weight average molecular weight of 5000 and a structural formula of CH ₂ ＣＲCR ₁ COO (CH ₂ ) _n.
—NHR ₂ R ₃ (wherein, n is an integer of 1 to 10, R ₁ , R
₂ , R ₃ is a weak base having 1 to 6 carbon atoms). The difference in particle size between carbon black and resin particles is (R _A + R
^{_{B) 2 / R B 2 =}} 765> is 121.

3. Synthesis of conductive plastic particles and preparation of sheet heating element Resin particles: 20 parts Carbon black dispersion: 5 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 10 parts of styrene in which 0.3 part of azobisisobutylnitrile was dissolved was added to this dispersion, and the mixture was subjected to 5000 r with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
The mixture was stirred for 10 minutes at pm, and reacted 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 polymer particles having an average particle diameter of 7.5 μm.

TEM as conductive layer and shape confirmation test
As a result of observation, as shown in FIG. 4 (c), it was confirmed that the particles were spherical polymer particles in which the conductive material was uniformly localized on the particle surface. When the resistance of the sample in which the particles were applied to glass fiber was measured by a constant current method, the resistance was as low as 120Ω, and good conductivity was confirmed. Also, in the moisture resistance test, it was found that it was extremely excellent with little water absorption in a high temperature and high humidity environment.

As shown in FIGS. 10 and 11, a planar heating element was assembled from the same sample and placed in the soil of a greenhouse, and the temperature distribution in the soil was kept uniform. Further, since the sheet heating element has excellent water resistance even in soil, no corrosion was observed for 3 years. [Example 5-2] Polymer particles having an average particle size of 8.0 µm were obtained in the same manner as in Example 5-1 except that the synthesis of the last conductive plastic particles was performed as follows. As a result of TEM observation as a shape confirmation test, FIG.
As shown in (b), the particle surface has a plurality of depressions,
In addition, it was confirmed that the polymer particles were deformed polymer particles in which the conductive substance was uniformly localized on the particle surfaces. When the resistance of the sample in which the particles were applied to glass fiber was measured by a constant current method, the resistance was as low as 130Ω, and good conductivity was confirmed. Also, in the moisture resistance test, it was found that it was extremely excellent with little water absorption under a high temperature and high humidity environment.

As shown in FIGS. 10 and 11, a planar heating element was assembled from the same sample and placed in the soil of a greenhouse, and the temperature distribution in the soil was kept uniform. Further, since the sheet heating element has excellent water resistance even in soil, no corrosion was observed for 3 years.

Synthesis of conductive plastic particles Resin particles: 20 parts Carbon black dispersion: 6 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 10 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile was added to this dispersion, and the mixture was subjected to 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
Then, the mixture was stirred 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. [Example 5-3] Polymer particles having an average particle size of 9.0 µm were obtained in the same manner as in Example 5-1 except that the synthesis of the last conductive plastic particles was performed as follows. As a result of TEM observation as a shape confirmation test, FIG.
As shown in (a), it was confirmed that the polymer particles were deformed and had a depressed portion on the particle surface and a conductive substance was uniformly localized on the particle surface.

The resistance of the sample in which the particles were applied to glass fiber was measured by a constant current method. As a result, a low value of 110Ω was observed, and good conductivity was confirmed. Also, in the moisture resistance test, it was found that it was extremely excellent with little water absorption under a high temperature and high humidity environment.

When the sheet heating element was assembled from the same sample as shown in FIGS. 10 and 11, and placed in the soil of a greenhouse, the temperature distribution in the soil was kept uniform. In addition, the sheet heating element did not corrode for 3 years because of its excellent water resistance even in soil.

Synthesis of Conductive Plastic Particles Resin particles: 20 parts Carbon black dispersion: 8 parts Ion-exchanged water: 430 parts These were mixed with a stirring rod to obtain a dispersion. Next, 10 parts of styrene obtained by dissolving 0.3 part of azobisisobutylnitrile was added to this dispersion, and the mixture was subjected to 5000 rpm with a homogenizer (TK AUTO homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.).
Then, the mixture was stirred 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. Example 5-4 A dispersion having an average particle size of 0.5 μm was obtained in the same manner as in Example 5-1 except that one part of acrylic acid was added in the synthesis of anionic resin particles.
Therefore, the difference in particle size between the resin particles and the carbon black is (R _A
+ R _B ) ² / R _B ² = 312> 121. Other conditions were the same as in Example 5-1, and the average particle size was 9.0 μm.
m of conductive plastic particles were obtained. As in Example 5-1, the resistance was low and the water resistance was good. [Examples 5-5, 6, 7] Particles were prepared in the same manner as in Example 5-1 except that γ-Fe ₂ O ₃ , CoFe ₂ O ₄ and CrO ₂ were used instead of carbon black. Conductive plastic particles having a diameter of 9.5 μm, 8.5 μm, and 9.0 μm were obtained. The resistance value is low as in Example 5-1.
The water resistance was also good. [Comparative Example 5-1] Styrene: 75 parts n-butyl acrylate: 5 parts Carbon black: 20 parts In a 1-liter four-necked flask, the stirring speed was 250 rpm.
m, a polymerization temperature of 70 ° C., a polymerization time of 8 hours, and after washing residual monomers with acetone and benzene, the resistance of a sample applied to glass fiber was measured by a galvanostatic method. Good conductivity was confirmed. However, in the moisture resistance test, water absorption was observed under a high temperature and high humidity environment because of a high carbon content. As shown in FIGS. 10 and 11, a sheet heating element was assembled as shown in FIGS. 10 and 11, and was placed in the soil of a greenhouse. Corrosion was observed in six months. [Comparative Example 5-2] In the same manner as in Example 5-1 except that the terminal group of the cationic oligomer was changed to a quaternary ammonium salt in the dispersion of carbon black, a conductive material having an average particle size of 7.5 μm was used. Although water-resistant plastic particles were obtained, the moisture resistance test revealed that moisture absorption was remarkable in a high-temperature and high-humidity environment, indicating poor water resistance. [Comparative Examples 5-3 and 4] In the synthesis of the conductive plastic particles, except that styrene was used in 4 parts and 14 parts,
Polymer particles were obtained in the same manner as in Example 5-1. However, although the polymer particles had good water resistance, styrene
In the case of the part, the amount of the reactive monomer was insufficient, and the carbon was not fixed on the surface. In the case where styrene was used as 14 parts, the resistance value was as high as 400 ohm in the conductivity test, and the conductivity was poor. [Comparative Example 5-5] 0.3% of the resin particles were
And microns, except that it has to be a difference in particle diameter of the resin particles and carbon black and ^{_{(R A + R B) 2}} / R B 2 = 121, was polymerized in the same manner as in Example 5-1, polymerization particles Has a submicron average particle size, and micron-sized polymer particles cannot be obtained.

Synthesis of Resin Particles Styrene: 16 parts n-butyl acrylate: 4 parts Acrylic acid: 1 part Ammonium persulfate: 1 part Ion-exchanged water: 79 parts Aqueous solution obtained by dissolving the above ammonium persulfate in the above ion-exchanged water , 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, and an average particle diameter of 0.3 μm.
m polymer particles were obtained. [Comparative Example 5-6] Polymerization was performed in the same manner as in Example 5-1 except that the oligomer used for carbon dispersion was sodium dodecylbenzenesulfonate. Micron-sized polymer particles were not obtained.

The following is a summary of the test results performed on the above-described Examples and Comparative Examples.

First Invention Table 1 Low-temperature fixability Friction resistance Moisture resistance Layer formability Size (R _A + R _B ) ² / R _B ² Example 1-1 − − − ○ 765> 121 Example 1 2 ○ ○ ○ ○ ○ 765> 121 Example 1-3 ○ ○ ○ ○ ○ 155> 121 Example 1-4 ○ ○ ○ ○ ○ ○ 765> 121 Example 1-5 ○ ○ ○ ○ ○ 765> 121 Example 1-6 ○ ○ ○ ○ ○ 765> 121 Comparative Example 1-1 − − − − × 765> 121 Comparative Example 1-2 − − − − × 121 = 121 Comparative Example 1-3 ○ × × × ○ 765> 121 Comparative Example 1-4 × ○ × ○ ○-Second Invention Table 2 Cleanability Moisture Resistance Deformability Size (W _A / W _B ) X (ρ _B / ρ _A ) Example 2-1--○ (FIG. 2) (a)) ○ 4.0 <5.4 <7.5 Example 2-2 − − ○ (Figure 2 (b)) ○ 4.4 Example 2-3 ○ ○ ○ ○ 6.5 Example 2-4 ○ ○ ○ ○ 6.5 Example 2 -5 ○ ○ ○ ○ 6.5 Example 2-6 ○ ○ ○ ○ 6.5 Example 2-7 ○ ○ ○ ○ 6.5 Comparative Example 2-1 − − − × 5.4 Comparative Example 2-2 − − − × 5.4 Comparative Example 2-3 × ○ × (Figure 2 (c)) ○ 7.5 Comparative Example 2-4 × ○ × (Figure 2 (c)) ○ 4.0 Comparative Example 2-5 ○ × ○ ○ 6.5 Comparative Example 2-6 ○ × ○ ○-Third invention Table 3 Low-temperature fixability Friction resistance Clean kinking resistance Moisture resistance Layer forming Deformability Mixing ratio * Example 3-1 ○ ○ ○ ○ ○ ○ 7.2 Example 3-2 ○ ○ ○ ○ ○ ○ 7.2 Example 3-3 ○ ○ ○ ○ ○ ○ 7.2 Example 3-4 ○ ○ ○ ○ ○ ○ 7.2 Example 3-5 ○ ○ ○ ○ ○ ○ 7.2 Comparative Example 3-1 ○ ○ × ○ ○ × 8.2 Comparative Example 3-2 ○ × ○ ○ × ○ − Comparative Example 3-3 × ○ × × ○ × − Comparative Example 3-4 ○ ○ × ○ ○ ○ 5.0 Comparative Example 3-5 ○ ○ × ○ ○ ○ 6.0 Comparative example 3-6 - - - - - - - Comparative example 3-7 - - - - - - - *) mixing _{ratio: 4.0 <(W A / W} B) × (ρ B / ρ A) 7.
5 and 5.0 <(W _A / W _B ) × (ρ _B / ρ _A ) <6.0 The fourth invention Table 4 Low-temperature fixability Conductive layer forming size ゛ (W _M / ρ _M ) / (W _A / ρ _A + W _B / ρ _B ) Example 4-1 ○ ○ ○ (Fig. 4 (c)) ○ 1.0 <2.9 <3.0 Example 4-2 ○ ○ ○ (Fig. 4 (b)) ○ 2.8 Example 4 -3 ○ ○ ○ (Fig. 4 (a)) ○ 2.6 Example 4-4 ○ ○ ○ (Fig. 4 (c)) ○ 2.9 Comparative example 4-1 × ○ × ○-Comparative example 4-2 ○ × × ○ 1.0 Comparative Example 4-3 ○ × ○ ○ 3.0 Comparative Example 4-4 − − − × − Comparative Example 4-5 − − − × − Fifth Invention Table 5 Conductivity Moisture Resistance Deformability Size II (W _M / ρ _M ) / (W _A / ρ _A + W _B / ρ _B ) Example 5-1 ○ ○ ○ (Fig. 4 (c)) ○ 1.0 <2.2 <3.0 Example 5-2 ○ ○ ○ (Fig. 4 (b) 2.2 Example 5-3 ○ ○ ○ (Fig. 4 (a)) ○ 2.1 Example 5-4 ○ ○ ○ (Fig. 4 (c)) ○ 2.2 Example 5-5 ○ ○ ○ (Fig. 4 (c) )) ○ 2.2 Example 5-6 ○ ○ ○ (Fig. 4 (c)) ○ 2.2 Example 5-7 ○ ○ ○ (Fig. 4 (c)) ○ 2 .2 Comparative Example 5-1 ○ × − − − Comparative Example 5-2 ○ × ○ ○ 2.2 Comparative Example 5-3 × ○ × ○ 1.0 Comparative Example 5-4 × ○ ○ ○ 3.0 Comparative Example 5-5 − − − × − Comparative Example 5-6 − − − × −

[0138]

As described above, according to the method of the present invention, granulation to a micron size and layer formation are satisfied at the same time, and the inclusion of the third component in the particle bonding portion occurs due to aggregation and granulation. Thus, it was possible to produce micron-sized multilayer polymer particles. This first solves the problem that the fixing temperature could not be increased due to the high hardness and softening point of the shell when the friction resistance was improved by core-shell or encapsulated toner. It was done. That is, it is possible to provide a polymerized toner having excellent friction resistance due to the filler layer and low temperature fixing properties due to the low softening point plastic resin, and also having excellent moisture resistance.

In addition, the toner produced by the polymerization method generally has a spherical shape, and has a problem of adversely affecting the cleaning property.
Deformation and irregular shape were desired, but the cohesion method had weak adhesion surface of particles and had a problem in friction resistance due to mechanical stress. Was a problem. On the other hand, according to the method of the present invention, because of the deformation of the spheres formed by granulation, the adhered surface is strong and micron-sized irregular polymer particles can be produced without using an organic solvent. Second, it is possible to provide a modified polymer toner having excellent cleaning properties and moisture resistance.

Third, the method for producing irregularly shaped polymer particles and the method for producing multilayer polymerized particles according to the present invention solves the problem of reduction in friction resistance due to deforming, is excellent in cleaning properties and moisture resistance, and is excellent in deformability. Nevertheless, a low-temperature fixing polymerized toner having excellent friction resistance can be provided.

Fourth, according to the method for producing conductive multilayer polymer particles of the present invention, there is no need to add a large amount of a conductive substance, so that a low-temperature fixing conductive toner that solves the problem of fixing temperature is provided. be able to.

Fifth, the added conductive material is uniformly localized on the surface, realizes an ideal state for exhibiting a conductive function, and has excellent moisture resistance without problems such as corrosiveness. And a sheet heating element made of conductive plastic particles.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a low-temperature fixable polymerized toner having a filler layer on its surface and having excellent wear resistance.

FIG. 2 is an SEM photograph of a modified polymerization toner having a concave portion on the surface and having excellent cleaning properties.

FIG. 3 is a schematic view of a low-temperature fixable polymerized toner having a surface filler layer and a surface depressed portion and having excellent cleaning properties and abrasion resistance.

FIG. 4 is an SEM photograph of a conductive toner and a plastic particle in which a conductive substance is localized on the surface.

FIG. 5 is a schematic sectional view of a color printer.

FIG. 6 is a cross-sectional view of the contact type non-magnetic one-component developing device used in FIG.

FIG. 7 is a sectional view of a contact type non-magnetic one-component developing device used in FIG. 5;

FIG. 8 is a schematic diagram of a charge developing method of a conductive toner.

FIG. 9 is a schematic diagram of a one-component developing method using a conductive toner.

FIG. 10 is a structural diagram of a conductive polymer planar heating element.

FIG. 11 is a structural diagram of a heat board.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 101 ... Filler 102 ... Filler layer 103 ... Low softening point resin 104 ... Low softening point resin 200 ... Developing device 201 ... Photoconductor 202 ... Charging device 203 ... Laser exposure device 204 ... Blade cleaning device 205 ... Static electricity removal 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 ... Depressed portion 302 ... Filler 303 ... Filler layer 304 ... Low softening point resin 305 ... Low softening point resin 401 ... Filler 402 ... Filler layer 403 ... Resin 501 ... Insulating layer 502 ... Photoconductive layer 503 ... Conductive toner 504 ... Unexposed part 505 ... Exposure part 601 ... Developing roller 602 ... Photoconductor 603 ... Conductivity Toner 604: toner layer 605 Doctor blade 701 ... heating element 702 ... electrode 703: insulating material 801 ... conductive polymer planar heating element 802: insulating material 803 ... heat insulating material 804 ... cushioning material 805 ... surface material

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yuka Nakamura 70 Yanagicho, Saiwai-ku, Kawasaki-shi, Kanagawa Prefecture Inside the Toshiba Yanagicho Plant (72) Inventor Eiichi Kaga 70 Yanagicho, Sai-ku, Kawasaki-shi, Kanagawa Prefecture Co., Ltd. In the Toshiba Yanagimachi Plant (56) References JP-A-1-265262 (JP, A) JP-A-56-59802 (JP, A) JP-A-4-209630 (JP, A) JP-A-62-61632 (JP, A) JP-A-62-266558 (JP, A) JP-A-2-178868 (JP, A) JP-A-51-10887 (JP, A) JP-A-59-1573 (JP, A) 4-309528 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 257/02 C08F 2/44 G03G 9/08

Claims (5)

(57) [Claims] 1. A shear flow or a stirring flow is applied to a dispersion liquid comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles and a filler. A method for producing micron-sized multilayer polymer particles having a filler layer containing the filler on the surface by granulating and integrating a polymerizable monomer, resin particles and a filler by a polymerization reaction, wherein the dispersion liquid an opposite polarity to the polar group the polar group and a filler dispersant resin particles in a particle diameter R _B of the particle diameter R _a filler of the resin _{particles, (R a + R B)} 2 / R B 2 > 121, wherein the hydrophobic part of the resin particles and the hydrophobic part of the dispersant of the filler have an unsaturated double bond. 2. A shear flow or a stirring flow is applied to a dispersion comprising a dispersion medium containing water and a polymerizable monomer having an unsaturated double bond, and a dispersoid containing particles A and B. A method for producing micron-sized multilayer polymer particles having at least one depression on the surface thereof by granulating and integrating the polymerizable monomer, particles A and particles B, and causing a polymerization reaction, A polar group and dispersant for particles B
Of the polar group are opposite polarity, the particle diameter _{R B} of the particle diameter _{R A} and particles B of particles ^{_{A, (R A + R B}} ) 2 / R B 2>
121, the specific gravity ρ _{A of} the particle _A , the specific gravity ρ _{B of} the particle _B , the weight W _{A of} the particle _A , and the weight W of the particle B.
Is _{B, 4.0 <W A / W} B) × (ρ B / ρ A)
7.5. A method for producing micron-sized irregularly polymerized particles, which satisfies the relationship of 7.5. 3. Applying a shear flow or a stirring flow to a dispersion liquid comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles, and a filler. A method of producing micron-sized multilayer polymer particles having a filler layer containing the filler and at least one depression on the surface by granulating and integrating the polymerizable monomer, resin particles and filler by a polymerization reaction. a is, the polar group the polar group and filler dispersant having the resin particles is opposite polarity, and the particle diameter R _B of the particle diameter R _a filler of the resin particles, (R _a + R _B) ² / R _B ²
> Satisfy the relation of 121, a specific gravity [rho _A of resin particles, a filler having a specific gravity [rho _B, the weight W _A of resin particles, and filler - weight W _{B is, 4.0 <(W A / W} B) × (ρ _B / _{ρ A)} <
5.0 and 6.0 <(W _A / W _B ) × (ρ _B / ρ _A ) <
7.5. A process for producing micron-sized irregularly-shaped and multilayered polymer particles, wherein the relationship of 7.5 is satisfied and the hydrophobic part of the resin particles and the hydrophobic part of the dispersant of the filler have an unsaturated double bond. 4. A shear flow or a stirring flow is applied to a dispersion liquid comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles, and a conductive substance. A method for producing micron-sized multilayer polymer particles having a conductive layer containing the conductive material on the surface by granulating and integrating the polymerizable monomer, resin particles, and conductive material by performing the polymerization reaction. And the poles of the resin particles
The polar group of the dispersant of the conductive group and the conductive substance is opposite polarity,
The particle diameter _{R B} of the particle diameter _{R A} and conductive substance of the resin ^{_{particles, (R A + R B)}} 2 / R B 2> 121 satisfy the relationship of the specific gravity [rho _A of the resin particles, the specific gravity of the conductive material [rho _B ,
Density [rho _M of the polymerizable _monomer, the weight W _A, the weight of the conductive material W _B, and the weight W of the polymerizable monomer of the resin particles
_{M is, 1.0 <W M / ρ M} ) / (W A / ρ A
+ W _{B /} ρ _B) meets <3.0 relationships are resin particles a thermoplastic resin, the hydrophobic portion of the hydrophobic portion and the conductive material of the dispersant of the resin particles are those having an unsaturated double bond A method for producing a conductive polymerized toner. 5. A shear flow or a stirring flow is applied to a dispersion liquid comprising a dispersion medium containing water and a dispersoid containing a polymerizable monomer having an unsaturated double bond, resin particles, and a conductive substance. By performing the above, the polymerizable monomer, resin particles, and the conductive substance are integrated by granulation, and the polymerization reaction is performed,
A method for producing micron-sized multilayer polymer particles having a conductive layer containing the conductive substance on the surface of the polymer particles, wherein the polar group of the resin particles and the polar group of the dispersant of the conductive substance are opposite polarities, the particle diameter _{R B} of the particle diameter _{R a} and conductive substance ^{_{particles, (R a + R B)}} 2 / R B 2> 121 satisfy the relationship, of resin particles gravity [rho _a, the conductive material density [rho _B , Specific gravity ρ _M of polymerizable monomer, weight W of resin particles
_A, weight _{W B} of the electrically conductive material, and the weight _{W M} of the polymerizable _{monomer, 1.0 <W M / ρ M} ) / (W A / ρ
_{A +} W _{B / ρ B)} meets <3.0 relationships, hydrophobic part of the hydrophobic portion and the conductive material of the dispersant resin particles are those having an unsaturated double bond, weakly polar groups of the resin particles A method for producing conductive plastic particles, wherein the conductive group is an acidic group and the polar group of the conductive substance dispersant is a weakly basic group.