JPH07120076B2 - Method for manufacturing toner for developing electrostatic image - Google Patents

Description

The present invention relates to a toner for developing an electrostatic charge image for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like.

[Conventional technology]

Conventionally, as the electrophotographic method, as described in U.S. Pat.No. 2,297,691 specification, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, a number of methods are known.
Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with a toner, and a toner image is formed on a transfer material such as paper, if necessary. After transfer, the image is fixed by heating, pressure, heating and pressurizing, solvent vapor, or the like to obtain a copy.

The toner is triboelectrically charged with positive or negative electric charge depending on the polarity of the electrostatic latent image to be developed. To triboelectrically charge the toner, the triboelectric charging property of the resin, which is one component of the toner, can be used, but this method cannot obtain a sufficient charge amount. Therefore, an image obtained by developing with such toner is apt to fog and becomes unclear. Therefore, in order to impart a sufficient triboelectric charging property to the toner, a substance called a charge control agent is generally added.

Charge control agents known in the art today include nigrosine, azine dyes, quaternary ammonium salts, and the like, which control the toner to have a positive charge property. On the other hand, examples of controlling the toner to be negatively charged include metal complex salts of monoazo dyes and metal complexes of salicylic acid such as Co, Cr and Fe. These are usually added to thermoplastics,
It is melt-dispersed by heat, finely pulverized, and adjusted to an appropriate particle size as needed before use.

However, since it is extremely difficult to uniformly disperse these charge control agents in the thermoplastic resin, there is a problem in that the triboelectric charge amount between the toner particles obtained by pulverization is different. . Therefore, various methods have been conventionally used to make the dispersion more uniform. For example,
The basic nigrosine dye is used by forming a salt with a higher fatty acid in order to improve the compatibility with the thermoplastic resin.
Often, the unreacted fatty acid or salt dispersion product is exposed on the toner surface and contaminates the carrier or the toner carrier. This causes a decrease in toner fluidity, fog, or a decrease in image density. On the other hand, in order to improve the dispersibility of the charge control agent in the resin, a method of mechanically pulverizing and mixing the charge control agent and the resin powder in advance and then hot-melt kneading is used.
However, the original dispersion failure cannot be avoided, and there is a long-awaited improvement for obtaining sufficient charge uniformity.

Further, JP-A-58-106554 proposes a method of coating a monodisperse spherical core with a polymer substance containing a colorant. One of them is a method in which a monodispersed spherical core is added to a solution of cyclohexane, methanol or the like in which a polymer substance and a colorant are dissolved or dispersed, and the solvent is removed to perform coating. Such a method requires a fairly low amount of polymeric material in the solvent to obtain a good coating, requires equipment to remove the solvent and is costly. Further, it is technically difficult to avoid agglomeration of particles at the stage when the solution is concentrated, and it requires special measures and crushing of agglomerates as described in the publication. Furthermore, it is necessary that the core is not soluble in such a solvent, while the coated polymeric material must be soluble in the solvent. As a result, there are significant restrictions on the material of the core and the material of the coated polymeric material. Further, as another method, a method of coating with a dispersion liquid (mainly an aqueous dispersion liquid) in which a polymer substance and a colorant are dispersed has been proposed. Similar to the method using a solvent, such a method requires a device for removing water and is disadvantageous in cost. Further, it is technically difficult to avoid agglomeration of particles at the stage when the dispersion is concentrated. Furthermore, it is necessary to disperse the core body in water, and an auxiliary material such as an emulsifier is required to disperse the strongly hydrophobic core body. Generally, such an emulsifier is a hydrophilic substance, which deteriorates triboelectric chargeability in a highly insulating toner. It has a bad effect especially in high humidity. It is therefore necessary to remove such emulsifiers, but they are preferably not used because they are technically difficult.

Further, as another method, there has been proposed a method in which powders of a polymer substance and a colorant are used to be dissolved by heating and coated. In such a method, as described in the text of the publication, the temperature is adjusted to a temperature low enough to avoid thermal agglomeration of the core as much as possible and to a temperature high enough to bond the polymer substance as the coating substance. Is required, and there is a statement that this temperature adjustment is important. This is intended to prevent mutual fusion of the cores due to heat, but the toner used in the electrophotographic method is heated, pressured or heated after transferring the toner image onto a transfer material such as paper. Although it is intended to obtain a copy by fixing with pressure or the like, a thermoplastic resin is mainly used as a material of the core body because of the necessity of melting by heat and / or pressure in the fixing step, and a polymer which is a coating substance. When the substance is heated and melted, a considerable amount of the core is thermally melted. When the polymer substance is entirely adhered to the particle surface of the core material, the core body is agglomerated due to the mold of the polymer substance even if heat melting of the core substance occurs during heating when adhering the polymer substance. Can be prevented to some extent. However, it is difficult to prevent thermal agglomeration of core particles due to thermal melting of the core when the coating material is partially adhered, and it is technically difficult to obtain a partially coated toner. Is.

In JP-A-61-210368, a resin for binder and a colorant are dispersed on the surface of spherical particles using a mixer such as a Henschel mixer or a super mixer, and the softening point of the binder resin is lower than the softening point of the spherical particles. A method of fixing by treating at a higher temperature has been proposed. This method has a material limitation that the binder resin is lower than the softening point of the spherical particles, and as shown in the examples.
It is technically difficult to avoid cohesive fusion of spherical particles due to heat treatment at 110 ° C. to 140 ° C. for 10 minutes, and it is also considered that thermal deterioration may occur depending on the material used,
It cannot be said that the problem has been solved sufficiently.

As described above, it is strongly required in the technical field to uniformly disperse the charge control agent in each toner particle.

[Problems to be solved by the invention]

An object of the present invention is to provide a method of manufacturing a toner that overcomes the above problems in the method of manufacturing a toner.

An object of the present invention is to provide a method for producing a toner that can be uniformly and stably charged.

[Means and Actions for Solving Problems]

The object of the present invention is to provide colored particles (A) having a softening point of 90 to 150 ° C., containing at least a binder resin and a colorant, and having a particle size ratio of 0.2 or less with respect to the colored particles (A) and being triboelectrically charged. The charge control resin particles (B) having a triboelectric charging property with an absolute value of 3 μc / g or more are formed from a rotating piece and a fixed piece under an atmosphere temperature of 30 to 70 ° C. and a minimum gap of 0.5 to 5 mm. 0.5-5mm formed from impact part or two kinds of rotating pieces with
Of the colored particles (A) by a mechanical impact by a rotating piece which passes through an impact part having the shortest gap of and rotates at a tip peripheral speed of 30 to 150 m / sec. It is an object of the present invention to provide a method for producing a toner for developing an electrostatic charge image, which comprises fixing the charge control resin particles (B) at a coverage of 0.1 to 50%.

Hereinafter, the present invention will be described in detail.

In the toner obtained by the production method of the present invention, the charge control agent or the charge control agent is firmly immobilized on the particle surface, and the toner is uniformly and stably present in each toner particle, so that the friction between the toner particles is extremely high. The amount of charge becomes uniform. On the other hand, by simply uniformly mixing the charge control agent and the toner base, the charge control agent adhering to the toner surface is easily desorbed during the continuous copying process, and the carrier or toner carrier is contaminated. Since the triboelectric charge amount is gradually decreased, the image density is decreased and the fog is increased, which is not preferable. Even in the case of a toner produced by conventional melting, kneading, pulverizing, and classifying, a part of the charge control agent tends to be desorbed due to its weak adhesion on the toner surface, and at the same time contaminates the carrier and the toner carrier. To do. Originally, the charge control agent is
Because of that function, it only needs to exist on the toner surface.
What is present in the toner particles is substantially wasted. It is considered that in the conventional toner production, most of the added charge control agent was wasted because it was only used.
Moreover, it was difficult to control the amount of the surface portion.

That is, there is a difference in the dispersibility depending on the kneading property and the kneading method of the binder resin and the charge control agent used, and for example, lowering the kneading temperature to improve the dispersibility is considered, but cutting or coloring of the binder resin Since the dispersibility of the agent tends to be poor, a kneading method preferable for the charge control agent is not always adopted. As a result, it is presumed that the amount of the toner surface portion changes due to the difference in the rupture method with respect to the impact during pulverization.

Also, in the case of a toner obtained by a suspension polymerization method, it is difficult to control the amount of the charge control agent on the surface portion at the same time as the toner obtained by kneading and pulverizing from the viewpoint of dispersibility. Moreover, it is considered that most of the added charge control agent was wasted because it was used only partially.

Particularly in such a method, a part of the charge control agent has a problem of polymerization inhibition like a metal complex salt of a nigrosine monoazo dye, which may make it difficult to use a large amount. In addition, hydrolyzable substances, those that decompose with monomers, those with strong hydrophilicity, etc., lose the charge controllability and broaden the particle size distribution,
In some cases, it may be difficult to use due to the formation of fine particle size. In the case of a capsule toner whose surface is coated with a resinous substance, a coating method using a resin solution is mainly used, and at the same time, it is equal due to problems such as uneven distribution of the charge control agent or the same problems as described above. It is not always technically easy to control such a surface.

The particles (B) having charge controllability and the colored particles (A) are powdery and partially immobilized on the colored particles (A) by mechanical impact.

In the insulating toner, it is important to adjust the triboelectric charge amount to be constant. That is, one important characteristic that a good image can be obtained even in different environments and that a good image that is the same as the initial image can be obtained even in continuous image output is how to control the triboelectric charge amount. is there. Generally, it is necessary to improve the rise of triboelectrification, the absolute amount of which tends to be large, and it is necessary to create a large electric field to transfer toner to the latent image surface due to the excessive electrostatic charge, especially in a low humidity environment. , There is a risk on the system and discharge due to insulation breakdown.

On the other hand, if the charging property is suppressed, especially in a high humidity environment,
It takes time to have a sufficient amount of charge, and toner other than the latent image portion cannot be removed by a force other than an electric force, which causes a problem that the image is contaminated. These problems can be solved by partially immobilizing the particles (B) having charge controllability on the surface of the colored particles (A). That is, the triboelectric charge amount is controlled by the antistatic effect because the charge control agent is present uniformly and partially on the toner particles. On the other hand, when the particles (B) having charge controllability are entirely present on the toner particles, the antistatic effect is small and the absolute amount of triboelectric charge (absolute value of triboelectric charge) becomes too large. Presumed.

The toner according to the present invention is one in which particles having charge controllability are fixed in a powder form by mechanical impact. Therefore, the toner subjected to the treatment of the present invention is subjected to a subsequent step, for example, when externally adding silica or the like. The toner acts as an integral unit without being substantially released by stirring, stirring during development, rubbing, or the like.

The amount of charge control agent on the toner surface is controlled by the added amount and is evenly present, so a uniform triboelectric charge amount is always obtained even during continuous copying, so that the image density is constant and the image quality is stable. An image is obtained.

Further, in the toner according to the present invention, the charge control agent can be present only on the surface of the toner.
It can be 1/5 or less (for example, about 1/10).

Further, since the charge control agent is fixed on the toner surface in the toner produced by such a method, carrier contamination and sleeve contamination are extremely small and good developing characteristics can be obtained.

As the particles (B) having charge controllability, either particles consisting of a charge controllable substance alone or resin particles in which a charge controllable substance is dispersed in a resin can be used.

The particles (B) and the colored particles (A) preferably have a value of (average particle size of particles (B) / average particle size of particles (A)) of 0.2 or less. When the particle size ratio is 0.2 or more, it is difficult to uniformly fix the particles (B) on the surface of the colored particles (A).

The coverage of the particles (B) (the ratio of the particles (A) surrounded by the particles (B)) is represented by the following formula.

The particle size distribution is measured by the following measuring method. Coulter counter TA-II type (manufactured by Coulter)
Alternatively, an ENZONE particle counter 80XY-2 (manufactured by US Particle Data Co., Ltd.) is used to output a number average distribution and a volume average distribution. A 1 to 4% NaCl aqueous solution is used as the electrolytic solution.

As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate as a dispersant is added to 100 to 150 ml of the aqueous solution of the electric field, and 0.5 to 50 mg of a measurement sample is further added.

The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and with the Coulter Counter TAII type or the Elzone Particle Counter 80XY-2, using 12 to 120μ aperture as an aperture, 0.2 to The particle size distribution of 40 μ particles is measured to obtain a volume average distribution and a number average distribution.

[In the formula, W ₁ represents the weight of the particles (A), and W ₂ represents the particles (B).
, R ₁ represents the average particle size of the particles (A), R ₂ represents the average particle size of the particles (B), M ₁ represents the true density of the particles (A), and M ₂ represents the particles. The true density of (B) is shown. The colored particles (A) have a coverage of 0.1 to 50% depending on the particles (B).
Is preferably coated with. Specifically, when the particles (B) are substantially formed of only the charge control substance, the coverage is 0.1 to 10%, preferably 0.2 to 5%. When the particles (B) are composed of the charge control substance and the resin component, 0.2 to 50%, preferably 0.4 to 40%
Is good.

If the coverage is 0.1% or less, the charge controllability is insufficient, while if it exceeds 50%, the absolute value of friction friction is too large and an image with high image density is obtained. The tendency to become less likely to be increased.

The charge controllable substance in the present invention means a substance satisfying the following triboelectric charging characteristics. That is, 5 parts by weight of the charge control material is heated to 100 ° to 150 ° C. with a heat roll for 100 parts by weight of a bulk polymer of polystyrene resin (weight average molecular weight of about 100,000 to 200,000).
The particles are sufficiently kneaded at, for example, about 30 minutes to 1 hour, cooled and pulverized, and then classified to obtain polystyrene particles containing a charge control substance having a main particle size of 10 μm. About 5 g of prepared polystyrene particles and 95 g of carrier iron powder (for example, EFV200 / 300 manufactured by Nippon Iron and Powder Co., Ltd.) which is not covered with a resin having a main particle size of 200 to 300 mesh is 25 ° C., 50 to 60.
After leaving it in the environment of% RH overnight, mix it thoroughly in a polyethylene container with a volume of about 200cc (for about 5 to 10 minutes), and use the aluminum cell with a 400 mesh screen for normal blow-off. The amount of tribo charge is measured by the method. The triboelectric charge measured by this method has an absolute value of 3 μc / g or more, particularly 7 μc / g or more.

As the charge control substance used in the toner of the present invention, a positive or negative charge control agent which is at least solid at a temperature of 20 to 90 ° C. is used.

(1) The following substances are used to control the toner to be positively charged.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes [eg,
CIBasic Yellow 2 (CI41000), CIBasic Yellow
3, CIBasic Red 1 (CI45160), CIBasic Red 9
(CI42500), CIBasic Violet 1 (CI42535), C.
I.Basic Violet 3 (CI42555), CIBasic Violet 10
(CI45170), CIBasic Violet 14 (CI42510),
CIBasic Blue 1 (CI42025), CIBasic Blue 3
(CI51005), CIBasic Blue 5 (CI42140), CI
Basic Blue 7 (CI42595), CIBasic Blue 9 (CI5
2015), CIBasic Blue 24 (CI52030), CIBasic
Blue 25 (CI52025), CIBasic Blue 26 (CI4404
5), CIBasic Green 1 (CI42040), CIBasic Gre
en 4 (CI42000)] etc., lake pigments of these basic dyes, (as a laker, phosphotungstic acid,
Phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide,
(Ferocyanide, etc.), CISovent Black 3 (CI26
150), Hansa Yellow G (CI11680), CIMordlant
Black 11, CI Pigment Black 1, benzolmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, or dialkyltin compounds such as dibutyl or dioctyl, dialkyltin borate compounds, guanidine derivatives, vinyl polymers containing amino groups, amino groups Polyamine resin such as condensation polymer contained.

(2) The following substances control the toner to be negatively charged. Japanese Patent Publication No. 41-20153, No. 43-27596, No. 44-6397
No. 45-26478, metal complex salts of monoazo dyes. Japanese Patent Sho 55-42752, Japanese Sho 58-41508, Japanese Sho 58
-7384, JP-B-59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, metal complexes of dicarboxylic acids such as Zn, Al, Co, Cr and Fe, and sulfonated copper phthalocyanine pigments.

Further, the charge controllable substance used in the present invention is required to have little environmental dependence, be thermally stable, be mechanically stable, and be chemically stable. .

As the resin used for the particles (B), a binder material for toner can be used. For example, homopolymers of polystyrene and its substitution products: styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer. Polymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-isobrene copolymer, styrene-
Styrene-based copolymers such as acrylonitrile-indene copolymers: acrylic resin, methacrylic resin, silicone resin, polyester resin, furan resin, epoxy resin,
Are exemplified. Preferred binder materials are cross-linked styrenic copolymers or polyesters. As a comonomer of this styrene-based copolymer, for example,
Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid Monocarboxylic acid having a double bond such as octyl acid, acrylonitrile, methacrylonitrile, acrylamide or the like, or a substituted form thereof: for example, a double bond such as maleic acid, butyl maleate, methyl maleate or dimethyl maleate. Dicarboxylic acid and its substitution product: Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used, and examples thereof include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and the like. Ethylene Call diacrylate, ethylene glycol dimethacrylate, 1,3-carboxylic acid ester divinyl aniline having two such double bonds, such as butanediol dimethacrylate, divinyl ether,
Divinyl compounds such as divinyl sulfide and divinyl sulfone and compounds having 3 or more vinyl groups are used alone or as a mixture.

Such a resin preferably has a Tg of 50 ° C. or higher, preferably 55 ° C. or higher for so-called blocking property for long-term storage. The kneading and pulverizing means of the charge control substance and the resin is particularly suitable for use in the resin when the charge control substance simple substance particles or aggregates of the simple substance particles have a particle size ratio to the particle (A) of 0.2 or more. It is an effective means because it can disperse a substance and pulverize it to 0.2 or less.

The ratio of the above-mentioned charge control substance to the resin is 50/50 to 1/99 of the weight of the charge control substance / the weight of the resin, preferably 2
0/80 to 1/99 is good.

In the case of resin particles (B) containing a charge controllable substance,
The charge control substance and the resin are melt-kneaded by heat, cooled, and pulverized by a generally known method to obtain fine particles. If necessary, fine particles having a preferred particle size may be obtained by classification. Alternatively, the composition of the resin and the charge control substance may be melted, and the melt may be heated and sprayed to form fine particles.

Further, polymerization is carried out in the presence of a charge control substance having no problems described above in an organic solvent in which a monomer is dissolved but a polymer produced from the monomer is not dissolved, to generate polymer fine particles having a charge control substance, The solvent may be removed to obtain the polymer fine particles.

Further, fine particles of a polymer produced from a monomer having the charge control substance by dispersing the charge control substance having no problems described above in the monomer and performing suspension polymerization in a medium in which the monomer is substantially insoluble. There is also a way to get. At this time, as the dispersant used for suspension polymerization, a dispersant such as silica or calcium phosphate is used. The dispersant is preferably removed from the polymer fine particles by washing with water or an acid / alkali, but it may not be removed from the polymer fine particles unless there is a practical problem.

In such pretreatment, the particles (B) are uniformly dispersed in the particles (A).
The fluidity and dispersibility of the particles (B) are important for adhering to the particles. That is, when the particles (B) exhibit strong agglomeration, individual particles cannot be formed in the pretreatment step, and uniform adhesion tends to be difficult. Similarly, when the fluidity is extremely poor, it is similarly difficult to form individual particles, and likewise, uniform adhesion is difficult. Regarding the particles (B) having poor fluidity and dispersibility, particles (B) having improved fluidity and dispersibility by previously adding and mixing silica fine powder to the particles (B).
It is particularly preferable to use the method for uniformly adhering the particles (B) to the particles (A) by using. As the fine silica powder used in such a method, positively charged treated silica is used for the positive charge control agent, and negatively charged treated silica is used for the negative charge control agent. The amount added is based on the weight of the particles (B)
0.01 to 10% by weight, preferably 0.1 to 5% by weight is used. As such treated silica, a hydrophobic silica fine powder treated with one or more of positively or negatively charged silane coupling agents, hydrophobic treating agents, silicone oil and the like is preferable. The silica fine powder preferably has a specific surface area of 40 to 400 m ² / g measured by a nitrogen gas adsorption method.
Further, treated silica fine powder having a hydrophobicity of 30 to 80% measured by a methanol titration test is particularly preferable.

The "methanol titration test" defined in this specification for evaluating the hydrophobicity of the treated silica fine powder is performed as follows. 0.2 g of the fine silica powder to be tested is added to 50 ml of water in an Erlenmeyer flask having a volume of 250 ml. Methanol is titrated from the bath until the total amount of silica is wet. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by suspending the total amount of silica fines in the liquid and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Next, it is a method of immobilizing, but in the toner, crushed pieces of the colored particles (A) and particles (B) are not liberated, and re-releasing of the particles (B) once adhered is not preferable, so that the toner is more reliably immobilized. Preferably.

It is important to control the impact force in a range where the colored particles (A) are not crushed and the temperature in a range where fusion cohesion does not occur. As an example of a fixing device for carrying out the present method, a pin mill (see Fig. 4-1) having a recycling function and a large number of rotating pins, a rotating blade or hammer (rotating piece) and a liner (fixing piece) It is effective to use a crusher that gives a shock between and has a recycling mechanism (see Figures 2-1 and 3-1).

The peripheral speed of the tip of the rotating piece in the device is preferably 30 to 150 m / sec. Although the temperature varies depending on the physical properties of the colored particles (A) and the particles (B), 30 ° C to 70 ° C is preferable, and the residence time of the impact part is 0.
2 sec to 12 sec is preferable. In the case of a pin mill, it is necessary to increase the concentration of powder. In the apparatus of the type shown in Fig.2-1 or Fig.3-1, the powder to be treated by centrifugal force is collected in the vicinity of the liner, so the latitude of the powder concentration is wide. The shortest gap between the pin mills or between the blade or hammer and the liner is preferably about 0.5 to 5 mm, and more preferably 1 mm to 3 mm, and good results are obtained.

More specifically, referring to FIG. 2-1, the powders (A) and (B) pretreated by the above-mentioned method are introduced into the inlet port 24.
From the inlet chamber 20 through the impacting portion 19 between the blade 15 and the liner 18 rotating along the rotating dispersion vane 14, through the outlet chamber 21, through the return path 22 and the blower 25, and again in the same circuit. Circulate. Eighth after the immobilization process is completed
Particles (A) having particles (B) having a morphology as shown in the figure are taken out from the product take-out port 23.

Here, the powder consisting of the particles (A) and the particles (B) is subjected to an impact between the blade 15 and the liner 18 at the impact part 19 to be fixed. Here, if necessary, it is preferable to flow cooling water through the jacket 26 to adjust the ambient temperature. In FIG. 2-2, the gap a between the blade 15 and the liner 18 is the shortest gap, and the space corresponding to the width b of the blade 15 is the impact portion.

Fig. 3-3 shows the rotor 3 rotating with the liner 29 of the fixing device.
1 shows the positional relationship between the liner 29 and the rotor 31.
Is the difference between the radii of two circles, a circle 51 obtained by connecting the tips of the protrusions to the inner circumference with the liner 29 and a locus 52 of the protrusions of the rotor 31. The same applies when a blade or a hammer is used instead of the rotor 31.

FIG. 4-2 is a schematic view of the pin in the pin mill type fixing device as seen from the front of the device, and the gap 55 between the fixed pin 39 and the rotating pin 54 is the shortest gap. Incidentally, 15 indicates the maximum gap, and 56 indicates the locus of the rotary pin 54.

The colored particles (A) are obtained, for example, by the following. As the colored particles (A) obtained by the pulverization method, a mixture of at least a binder resin, a colorant and, if necessary, a release agent is melt-kneaded, cooled and then pulverized by a generally known pulverizer, and if necessary, classified. Use the one with a uniform particle size distribution. The volume average particle diameter of the colored particles (A) preferable as the developing toner is 2 to
20μ.

Examples of the binder material for toner include homopolymers of polystyrene and its substitution products; styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers. Styrene-based copolymers such as styrene-isoprene copolymer and styrene-acrylonitrile-indene copolymer; acrylic resin, methacrylic resin, silicone resin, polyester resin, epoxy resin and the like can be used. Preferred binder materials are cross-linked styrene copolymers or polyester resins. Examples of the comonomer of this styrene-based copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate,
A monocarboxylic acid having a double bond such as acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof, for example, having a double bond such as maleic acid, butyl maleate, methyl maleate or dimethyl maleate. One or more vinyl monomers such as dicarboxylic acid and its substitution product are used. Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used, and examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, such as ethylene glycol diacrylate and ethylene glycol diethylene. Carboxyl ester having two double bonds such as methacrylate and 1,3-butanediol dimethacrylate Divinylaniline, divinyl compounds such as divinyl ether, divinyl sulfide and divinyl sulfone, and 3 or more vinyl groups The compounds are used alone or as a mixture.

Next, the colorant will be described. To produce magnetic toner, magnetic particles are added. In this case, the magnetic particles also serve as a coloring agent. As the magnetic particles that can be used in the present invention, substances that are placed in a magnetic field and magnetized are used.
Examples thereof include powders of ferromagnetic metals such as iron, cobalt and nickel, and powders of alloys and compounds such as magnetite, hematite and ferrite. Particle size is 0.1-1μ
m, preferably 0.1-0.5 μm magnetic particles are used. The content of the magnetic particles is 10 to 65 based on the weight of the toner.
%, Preferably 20-60% by weight. Further, these magnetic fine particles may be treated with a treating agent such as a silane coupling agent or a titanium coupling agent, or an appropriate reactive resin. In this case, although depending on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, a sufficiently preferable dispersibility can be obtained with a treatment amount of 5% by weight or less (preferably 0.1 to 3% by weight).

When the charge control substance is a resin, the resin is pulverized by a generally known method to obtain fine particles. If necessary, classification may be carried out to obtain preferable fine particles. Fine particles may be obtained by heating and spraying.

Further, it is possible to obtain fine particles from which the solvent has been removed by polymerizing in a solvent in which the monomer is dissolved or the polymer is not dissolved.
Fine particles may be obtained by polymerizing such a monomer composition in a medium in which the monomer is not substantially dissolved. At this time, a known dispersant is usually used. The dispersant is preferably used after being washed with water or removed with an acid, an alkali or the like, but may be used without being removed if there is no practical problem.

Next, the method for producing the toner of the present invention will be described in detail below.

The immobilization method according to the present invention includes a pretreatment in which the particles (B) are dispersed and uniformly adhered to the colored particles (A), and the adhered particles (B) are immobilized on the colored particles (A) by an impact force. Has a step of

In the pretreatment, while the particles (B) are dispersed, the particles (B) are rubbed with the colored particles (A) and attached to the colored particles (A) by an electrostatic force (and Juan der Waalska). Generally, a mixer with a high-speed stirring blade is used, but any mixer having a mixing function and a dispersing function may be used.

FIG. 1 shows an example of a mixer with a high-speed stirring blade. As a pretreatment, both the colored particles (A) and the particles (B) are well dispersed and the colored particles (A) are destroyed. It is necessary that the pulverization of the above is substantially not performed.

Therefore, the pretreatment temperature of the colored particles (A) and the particles (B) (material for toner) is 0 to 50 ° C., preferably 15 to 35 ° C., although it depends on the physical properties of this material. The peripheral speed of the tip is preferably 5 to 50 m / sec, and the processing time is preferably about 1 minute to 1 hour. When such pretreatment is carried out, the temperature rises due to agitation, so cooling with a jacket or cooling the inside of the tank by introducing cooling air is preferred. The pretreatment device does not have to be a mixer with a high-speed stirring blade, but may have a dispersing function and a mixing function and can obtain a sufficiently long residence time. It is also good to drop it. In addition to the above, the particles (B) may be dispersed in a liquid containing the colored particles (A), filtered, and dried to perform pretreatment.

As the colorant, conventionally known dyes, carbon black, and pigments such as grafted carbon black in which the surface of carbon black is coated with resin can be used. The colorant is preferably contained in an amount of 0.5 to 30% by weight based on the binder resin.

The colored particles (A) obtained by the polymerization method can be obtained, for example, by the method shown below, but the invention is not limited thereto.
An aqueous phase containing a suspension stabilizer of a monomer system in which a polymerizable monomer, a colorant, a polymerization initiator, and optionally a crosslinking agent, a charge control agent, a polar polymer, and other additives are uniformly dissolved or dispersed ( That is, it is charged into the continuous phase) and granulated and polymerized with stirring. After that, the suspension stabilizer is removed, and the product is obtained by filtering and drying.

It is particularly preferable to obtain the particles (A) by the suspension polymerization method described below because the particle size distribution is sharp.

The polymerizable monomer applicable to form the polymerized colored particles (A) is a monomer having a CH ₂ ═C <group as a reactive group, and is styrene, o-methylstyrene, m-methylstyrene, p-methyl. Styrene p-methoxystyrene, p
-Styrene such as ethylstyrene and its derivatives: acrylic acid, methacrylic acid, maleic acid, maleic acid half ester: methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate , Acrylic acid esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate: vinyl groups such as acrylonitrile, methacrylonitrile, acrylamide and other acrylic acid or methacrylic acid derivatives There are monomers having a reactive double bond such as These may be used alone or in combination of two or more. You may use a crosslinking agent as needed. Examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate and the like. The amount of the crosslinking agent added is usually 100 polymerizable monomers.
0.1 to 5 parts by weight is used with respect to parts by weight. Further, a polymer of these polymerizable monomers may be added in a small amount in the monomer composition. Among the above-mentioned monomers, polymerized colored particles (A) produced from styrene, styrene having a substituent such as an alkyl group, or a mixed monomer of styrene and another monomer have developability, It is preferable in consideration of durability.

Further, a preferable polymerized toner can be obtained by adding a polar polymer having a polar group, a polar copolymer or a cyclized rubber as an additive at the time of polymerizing the monomer to polymerize the polymerizable monomer. The polar polymer, polar copolymer or cyclized rubber may be added in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, based on 100 parts by weight of the polymerizable monomer. If the amount is 0.5% by weight or less, it is difficult to obtain a sufficient pseudocapsule structure, and if the amount is 50 parts by weight or more, the amount of the polymerizable monomer is insufficient and the properties of the polymerized toner tend to deteriorate. Polar polymer,
It is preferable to polymerize by suspending a polymerizable monomer composition containing a polar copolymer or a cyclized rubber in an aqueous phase of an aqueous medium in which the polar polymer and a dispersant having an opposite charge property are dispersed. . That is, the cationic or anionic polymer, the cationic or anionic copolymer or the anionic cyclized rubber contained in the polymerizable monomer composition is a reversely charged anion dispersed in an aqueous medium. Of a polar or cationic copolymer by adding a polar or cationic dispersant electrostatically to the surface of the toner particles to prevent the particles from coalescing and stabilizing by covering the surface of the particles with a dispersant. Alternatively, since the cyclized rubber gathers on the surface layer of the particles serving as the toner, it becomes a kind of shell-like form, and the obtained particles become pseudo capsules. Then, since the relatively high molecular weight polar polymer, polar copolymer or cyclized rubber gathered in the particle surface layer portion encloses a large amount of the low softening point compound inside the toner particles,
It imparts excellent properties of blocking property, developing property and abrasion resistance to the polymer particles of the present invention. The polar polymers (including polar copolymers and cyclized rubbers) and reversely-charged dispersants that can be used in the present invention are exemplified below. The polar polymer having a weight average molecular weight of 5,000 to 500,000 measured by GPC dissolves well in the polymerizable monomer and has durability, and thus is preferably used.

(I) As the cationic polymer, a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate or diethylaminoethyl acrylate, a copolymer of styrene and the nitrogen-containing monomer or styrene, an unsaturated carboxylic acid ester, etc. And the nitrogen-containing monomer.

(Ii) Examples of anionic polymers include polymers of nitrile-based monomers such as acrylonitrile, polymers of halogen-containing monomers such as vinyl chloride, polymers of unsaturated carboxylic acids such as acrylic acid, and unsaturated dicarboxylic acids. There are polymers of basic acids, polymers of unsaturated dibasic acid anhydrides, or copolymers of styrene and the monomers.

As the dispersant, an inorganic fine powder which has the ability to disperse and stabilize the monomer composition particles in an aqueous medium and is sparingly soluble in water is preferable. The amount of dispersant added to the aqueous medium is based on water.
It is preferable to add 0.1 to 50% by weight (preferably 1 to 20% by weight).

(Iii) As the anionic dispersant, Aerosil # 200,
There are colloidal silica such as # 300 (manufactured by Nippon Aerosil Co., Ltd.).

(Iv) Examples of the cationic dispersant include aluminum oxide, magnesium hydroxide, and hydrophilic positively charged silica fine powder such as aminoalkyl-modified colloidal silica treated with a coupling agent.

Instead of the above polar polymer or copolymer, a cyclized rubber having anionic property may be used.

To produce the magnetically polymerized colored particles (A), the magnetic particles are added to the monomer composition. In this case, the magnetic particles also serve as a coloring agent. As the magnetic particles that can be used in the present invention, substances that are magnetized by being placed in a magnetic field are used. For example, powders of ferromagnetic metals such as iron, cobalt and nickel, or magnetite, hematite, alloys and compounds such as ferrite are used. Powder is included. Particle size is 0.05-5 μm,
Preferably, magnetic fine particles having a size of 0.1 to 1 μm are used. The content of the magnetic particles is 10 to 60 relative to the weight of the toner.
%, Preferably 20-50% by weight. Further, these magnetic fine particles may be treated with a treating agent such as a silane coupling agent or a titanium coupling agent, or an appropriate reactive resin. In this case, depending on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, a treatment amount of 5% by weight or less (preferably 0.1 to 3% by weight) is sufficient to obtain a polymerizable monomer and a low softening point compound. Dispersibility is obtained and the physical properties of the colored particles (A) are not adversely affected. Polymerized colored particles (A)
Contains a coloring agent, and as the coloring agent, conventionally known dyes, carbon black, and pigments such as grafted carbon black in which the surface of the carbon black is coated with a resin can be used. The colorant is contained in an amount of 0.5 to 30% by weight based on the polymer and the low softening point compound. If necessary, a charge control agent and a fluidity modifier high-profile agent may be added (internally added) to the toner.

Suspension polymerization method, a colorant or a monomer composition in which the additives added as necessary are uniformly dissolved and dispersed, 0.1 ~ 5
In an aqueous medium containing 0% by weight of a suspension stabilizer (eg, a sparingly soluble inorganic dispersant) (eg, heated to a temperature of 5 ° C or higher, preferably 10 ° C to 30 ° C or higher than the polymerization temperature). The mixture is dispersed with an ordinary stirrer, a homomixer, a homogenizer or the like. Preferably, the particles of dissolved or softened monomer composition are of the desired toner particle size, generally 30
The stirring speed, time and temperature of the aqueous medium are adjusted so as to have a size of not more than μm (for example, a volume average particle size of 0.1 to 20 μm). Then, the liquid temperature of the aqueous medium is lowered to the polymerization temperature while stirring is performed to such an extent that the sedimentation of the particles is prevented so that the state is almost maintained by the action of the dispersion stabilizer. The polymerization temperature is set to 50 ° C. or higher, preferably 55 to 80 ° C., particularly preferably 60 to 75 ° C., and the polymerization is carried out by adding a substantially water-insoluble polymerization initiator while stirring. After the completion of the reaction, the produced toner particles are collected by an appropriate method such as washing, removal of the dispersion stabilizer, filtration, decantation, centrifugation, etc. and dried to obtain polymerized colored particles (A) usable in the present invention. can get. In the suspension polymerization method, usually 200 to 3000 water per 100 parts by weight of the polymerizable monomer and low softening point compound.
Parts by weight are used as aqueous dispersion medium.

Further, it is preferable that the particles are made into fine particles in a molten state after being heated and mixed. Various conventionally known liquid atomization methods can be applied. That is, a one-fluid nozzle by pressure, a two-fluid nozzle by high-pressure air flow, a disc atomizer using a rotating disc, or the like may be used.

The particles (A) used in the present invention have a softening point of 90 to 150 measured by the following method when the fixing method is for heat fixing.
C. is preferable, and a softening point of 90 to 140.degree. C. is particularly preferable.

A flow tester CFT-500 type (manufactured by Shimadzu Corp.) is used, and a sample of 60mesh bath product is weighed in an amount of about 1.0 to 1.5 g, and this is pressed with a molding machine at an amount of 100 Kg / cm ² for 1 minute. A flow tester measurement is performed on this pressurized sample under the following conditions, and the temperature corresponding to 1/2 of the stroke difference at the start of outflow and the end of outflow is taken as the softening point.

Measurement conditions RATE TEMP 5.0D / M (℃ 1 minute) SET TEMP 50.0DEG (℃) MAX TEMP 200.0DEG INTERVAL 2.5DEG PREHEAT 300.0SEC (sec) LOAD 50.0KGF (Kg) DIE (DIA) 0.5MM (mm) DIE ( LENG) 1.0MM PLUNGER 1.0CM ² (cm ² ) Waxes such as polyethylene wax, polyethylene oxide, paraffin, fatty acid, fatty acid ester, fatty acid amide, fatty acid metal salt, and higher alcohol when used as pressure fixing capsule toner. Ethylene-vinyl acetate resin, cyclized rubber and the like can be used. After being mixed by heating, fine particles may be formed in a molten state. Various conventionally known liquid atomization methods can be applied. That is, a one-fluid nozzle using pressure, a two-fluid nozzle using high-temperature airflow, a disk atomizer using a rotating disk, or the like may be used. Further, it may be melted by heating in a solvent and cooled to form fine particles. Here, it is also possible to use a dispersant while stirring. If necessary, the dispersant is preferably washed with water and removed with an acid or an alkali. This granulation method is preferable because spherical particles can be obtained.

Examples of the capsule wall forming substance include the following. Polystyrene, poly-α-methylstyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene- Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer, etc.), styrene-methacrylic acid ester Copolymers (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer,
Styrene-phenyl methacrylate copolymer, etc.), styrene-based resins such as styrene-acrylonitrile-acrylic acid ester copolymer (styrene or a styrene-substituted homopolymer or copolymer); rosin-modified maleic acid resin,
Epoxy resin, polyester resin, ionomer resin,
Examples include ketone resins and xylene resins.

The capsule wall forming method is a method of changing the solubility characteristics of the wall material in a solvent that dissolves the wall material but does not substantially dissolve the core material particles, for example, a phase in which a poor solvent is dropped to precipitate the wall substance. A separation method is preferably used.

When the particles (B) are uniformly fixed on the colored particles (A), the colored particles (A) are preferably spherical particles having few protrusions so as to uniformly fix the particles (B).

The toner obtained by the manufacturing method of the present invention can be applied to a known dry electrostatic image developing method. For example, a two-component developing method such as a cascade method, a magnetic brush method, a microtoning method, a two-component AC bias developing method: a conductive one-component developing method, an insulating one-component developing method, a jumping developing method or the like is used. One-component developing method; powder cloud method and fur brush method; non-magnetic one-component developing method in which toner is carried to a developing unit by being held on a toner carrier by electrostatic force and is used for development; electric field curtain method The present invention can be applied to an electric field curtain developing method in which toner is conveyed to a developing unit and provided for development.

Example-1 The above components were mixed with an attritor at a temperature of 60 ° C. for 4 hours to prepare a monomer composition. In the obtained monomer composition
2,2'-Azobis- (2,4-dimethylvaleronitrile) 10
Parts by weight and 1 part by weight of 2,2'-azobisisobutyronitrile were added and mixed, and the resulting mixture was Aerogel # 200.
(Manufactured by Nippon Aerosil Co., Ltd.) Add 10 parts by weight of ion-exchanged water heated to 60 ° C. to 1200 parts by weight of an aqueous medium under agitation of a TK homomixer, and agitate for 25 minutes at 10,000 rpm for dispersion granulation. did. In addition, change the paddle blade stirring to 60
The mixture was stirred at 0 ° C for 10 hours to complete the polymerization. Then, it was cooled, washed with a sodium hydroxide solution to dissolve and remove silica, washed with water, dehydrated, dried and classified to obtain particles (A) having a volume average diameter of 11 μm. The softening point was 115 ° C.

On the other hand, particles (B) were obtained by the following method.

The above mixture was kneaded with a roll mill at 120 ° C., cooled, coarsely pulverized with a speed mill, then finely pulverized with a jet mill, and classified with an air classifier to obtain particles (B) having a volume average diameter of 1 μm.

Next, 100 parts by weight of the particles (B) were mixed with 2 parts by weight of fine silica powder (BET specific surface area = 130 m ² / g) treated with aminosilicon oil.

Then, 50 parts by weight of the mixture consisting of particles (B) and silica fine powder was added to 1000 parts by weight of particles (A) using the apparatus shown in FIG.
Pretreatment was performed for 2 minutes at 30 m / sec.

Next, using the device shown in Fig. 2-1, the peripheral speed of the blade with the shortest clearance of 1 mm
The treatment was performed at 60 m / sec for a treatment time of 3 minutes (the residence time of the impact part was 2 seconds). The temperature inside the machine was 50 ° C. The coverage is
It was 13.7%.

When observed with an electron microscope, it was observed that they were partially fused and fixed. The triboelectric charge was +15 μc / g. 0.5 parts by weight of colloidal silica treated with amino silicone oil was externally added to 100 parts by weight of the above toner.

In the above developer, mixed with 1000 parts by weight of ferrite particles of 250 to 300 mesh coated with a silicone resin,
Images were printed using Canon Copier NP-3525. In continuous copying up to 30,000 sheets, good images were obtained without fogging, and good images with an image density of 1.3 were obtained without image deletion.

Example-2 The above components were mixed with an attritor at a temperature of 60 ° C. for 4 hours to prepare a monomer composition. 2, in the obtained monomer composition
10 parts by weight of 2'-azobis- (2,4-dimethylvaleronitrile) and 1 part by weight of 2,2'-azobisisobutyronitrile were added and mixed to obtain an amino-modified silica (Aerosil # 200 100 parts by weight treated with 5 parts by weight of aminopropyltriethoxysilane) 10 parts by weight and ion-exchanged water heated to 60 ° C. containing 15 parts by weight of 0.1N hydrochloric acid 12
The mixture was added to 00 parts by weight of an aqueous medium with stirring by a TK homomixer, and after the addition, the mixture was stirred for 15 minutes at 10,000 rpm to carry out dispersion granulation.
Further, stirring was changed to paddle blade stirring, and stirring was carried out at 60 ° C. for 10 hours to complete the polymerization. Then, the mixture was cooled, washed with a sodium hydroxide solution to dissolve and remove the amino-modified silica, washed with water, dehydrated, dried and classified to obtain particles having a volume average diameter of 11μ. The softening point was 120 ° C.

Particles (B) were obtained by the following method.

The polymerizable monomer composition was heated to 130 ° C., cooled with stirring, and kept at 60 ° C. A monomer composition was prepared by adding 3 parts by weight of 2,2'-azobis- (2,4-dimethylvaleronitrile).

Amino-modified silica (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.)
12 parts by weight of 100 parts by weight of 5 parts by weight of aminopropyltriethoxysilane and 600 parts by weight of distilled water, 1
Add the prepared monomer composition to a stainless steel container with a capacity of 2 liters containing 30 parts by weight of 10N base and stir at 60 ° C for 60 minutes at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). Was pre-dispersed to prepare a dispersion. This dispersion was granulated at a discharge pressure of 400 Kg / cm ² using a piston type high pressure homogenizer (manufactured by Gorin Co., model 15M-8TA). The time required for granulation was 5 minutes. After granulation, use paddle stirring blade for 10 hours at 60 ℃
Polymerization was completed by stirring under the conditions of. Then cool down,
The particles were obtained by washing with a sodium hydroxide solution, dehydration and drying. Tg was 90 ° C. The obtained particles had a volume average diameter of 1.2μ.

1000 parts by weight of particles (A) and 50 parts by weight of particles (B) were treated at 30 μ / sec for 5 minutes using the apparatus shown in FIG.
Using the device shown in the figure, the shortest gap was 1 mm, and the treatment was performed at 60 m / sec for 3 minutes (the residence time at the impact part was 2 seconds). The temperature inside the machine was 50 ° C. The coverage was 11.5%. The coverage was 11.5%.

When observed with an electron microscope, it was observed that they were partially fused and fixed. The triboelectric charge was -12 μc / g.

0.5 part by weight of colloidal silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to 100 parts by weight of the above toner.

The surface of 100 parts of ferrite particles having a particle size of 250 to 300 mesh was coated with 0.8 part of silicone resin to obtain magnetic particles.
When 10 parts of each of the above toners and 100 parts of magnetic particles were mixed and put into the developing device of FIG. 5 and developed, the image density was 1.
3 good images were obtained.

As described above, the developing device shown in FIG. 5 was used.

In the apparatus of the embodiment, the photosensitive drum 103 is 60 m in the direction of arrow a.
It rotates at a peripheral speed of m / sec. 122 is stainless steel with an outer diameter of 32 mm and a thickness of 0.8 mm that rotates at a peripheral speed of 66 mm / sec in the direction of arrow b (S
A sleeve made of US304), the surface of which was subjected to irregular sand plast using # 600 alundum abrasive grains so that the roughness of the circumferential surface was 0.8 μm (Rz =).

On the other hand, a ferrite sintered type magnet 123 is fixedly arranged in the rotating sleeve 112, the magnetic pole arrangement is as shown in FIG. 5, and the maximum value of the surface magnetic flux density is about 800 gauss. The non-magnetic blade 124 is made of non-magnetic stainless steel having a thickness of 1.2 mm. The blade sleeve gap was 400 μm.

On the surface of the photosensitive drum 3 facing the sleeve 122,
As an electrostatic latent image, a charge pattern of +150 V in the dark part and +150 V in the bright part was formed, and the distance from the sleeve surface was set to 300 μm. Then, a frequency of 800 Hz is applied to the sleeve by the power supply 134,
Development was performed by applying a voltage having a peak-to-peak value of 1.4 KV and a center value of +300 V.

A good image with an image density of 1.3 was obtained, and the image density did not decrease even in continuous image formation.

Example-3 The above components were mixed with an attritor at a temperature of 60 ° C. for 4 hours to prepare a monomer composition. To the obtained monomer composition 2.
10 parts by weight of 2'-azobis- (2.4-dimethylvaleronitrile) and 1 part by weight of 2.2'-azobisisobutyronitrile are added and mixed to obtain a calcium phosphate salt obtained from sodium phosphate and calcium chloride. After adding TK homomixer to 1,200 parts by weight of ion-exchanged water heated to 60 ° C containing 20 parts by weight under stirring of TK homomixer, 25
Granulated by stirring at 10,000 rpm for a minute. Further, stirring was changed to paddle blade stirring, and stirring was carried out at 60 ° C. for 10 hours to complete the polymerization. Then, the mixture was cooled and washed with 1 / 10N hydrochloric acid to dissolve and remove calcium phosphate, and the mixture was aqueous, dehydrated, dried and classified to obtain particles (A) having a volume average diameter of 11.5μ. Classification yield is 70% by weight
And the softening point was 125 ° C.

Particles (B) were obtained by the following method.

The above mixture was kneaded with a roll mill at 120 ° C., cooled, coarsely pulverized with a speed mill, then finely pulverized with a jet mill, and particles having a volume average diameter of 1 μm were obtained with an air classifier. 2μ or more was 5% or less.

Particles (A) (1000 parts by weight) and particles (B) (60 parts by weight) were treated at 30 m / sec for 5 minutes using the apparatus shown in FIG.

Then, using the device shown in Figure 2-1, the shortest gap 1mm, 60m / sec,
It was processed for 3 minutes (the residence time of the impact part was 2 seconds). The temperature inside the machine was 50 ° C. The coverage of the particles (A) with the particles (B) was 17.3%.

When observed with an electron microscope, it was observed that they were partially fused and fixed. The triboelectric charge was -13 μccg.

0.5 part by weight of colloidal silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) was externally added to 100 parts by weight of the above toner. Also, particle size 250
Magnetic particles were obtained by coating the surface of 100 parts by weight of ferrite particles between 0.8 and 300 mesh with 0.8 parts by weight of silicone resin.

When 10 parts by weight of the above toner and 100 parts by weight of magnetic particles were mixed and put into the developing device of FIG. 5 and developed, a good image was obtained. Good results were obtained even in continuous image output.

Example-4 The above components were mixed with an attritor at a temperature of 60 ° C. for 4 hours to prepare a monomer composition. To the obtained monomer composition 2.
10 parts by weight of 2'-azobis- (2.4-dimethylvaleronitrile) and 1 part by weight of 2.2'-azobisisobutyronitrile were added and mixed, and 10 parts by weight of Aerosil # 200 (manufactured by Nippon Aerosil) were included. The mixture was put into an aqueous medium of 1200 parts by weight of ion-exchanged water heated to 60 ° C. under stirring with a TK homomixer, and after the addition, the mixture was stirred at 10,000 rpm for 25 minutes to carry out dispersion granulation.

Further, stirring was changed to paddle blade stirring, and stirring was carried out at 60 ° C. for 10 hours to complete the polymerization. Then, the mixture was cooled, washed with a sodium hydroxide solution to remove the solvent from silica, washed with water, dehydrated and classified to obtain particles (A) having a volume average diameter of 11 μm. Softening point is 11
It was 5 ° C.

Particles (B) were obtained by the following method.

The above mixture was kneaded with a roll mill at 120 ° C., cooled, coarsely pulverized with a speed mill, then finely pulverized with a jet mill, and particles having a volume average diameter of 1 μm were obtained with an air classifier.

Particles (A) (1000 parts by weight) and particles (B) (50 parts by weight) were treated at 30 m / sec for 5 minutes using the apparatus shown in FIG.

Then, using the device shown in Figure 2-1, the shortest gap 1mm, 60m / sec,
It was processed for 3 minutes (the residence time of the impact part was 2 seconds).

The in-machine temperature was 50 ° C and the coverage was 13.8%.

When observed with an electron microscope, it was observed that they were partially fused and fixed. The triboelectric charge was +15 μc / g.

To 100 parts by weight of the above toner, 0.5 parts by weight of colloidal silica treated with amino silicone oil was externally added.

Images were printed with the above developer using a Canon copier NP-3525. Even in continuous copying, there was no fog and it was good, and good images were obtained without image deletion.

Example-5 After heat-kneading the components of the above formulation with a roll mill (150 ° C) for about 30 minutes and cooling the resulting kneaded product, use a pulverizer to add about 10μ
The particles (A) of the present invention were obtained by pulverizing to m (volume plane diameter) and finely cutting with a zigzag classifier manufactured by Alpine Co., so that the volume average particle diameter was about 12 μm. The softening point was 125 ° C.

To 1000 parts by weight of the particles (A), the particles (B) 40 of the above-mentioned Example 4 are added.
Parts by weight were treated for 5 minutes at 30 m / sec using the apparatus shown in FIG. Then, using the equipment shown in Figure 2-1, the shortest gap of 1 mm 60 m / se
c The treatment was carried out for 5 minutes (the residence time of the impacted part was 3.45μ).
The in-machine temperature was 55 ° C and the coverage was 16.2%.

When observed with an electron microscope, it was observed that they were partially fused and fixed. The triboelectric charge amount was +14 μc / g.

0.5 parts by weight of colloidal silica treated with amino silicone oil was externally added to 100 parts by weight of the above toner. Images were printed using the above developer with a Canon copying machine NP-3525. There is no fog in continuous copying, which is good,
A good image was obtained without image deletion.

Example-6 1000 parts by weight of the particles (A) of Example-2 were treated with 5 parts by weight of a Cr complex of diethyl salicybutylsalicylic acid at 30 m / sec for 10 minutes using the apparatus shown in FIG. Then, using the apparatus shown in FIG. 2-1, the shortest gap was 1 mm, the speed was 60 m / sec, and the treatment was carried out for 6 minutes (the residence time in the impact part was 4 seconds). The in-machine temperature was 60 ° C. and the coverage was 1.3% (average particle size 1 μ, density 1.1). When images were printed in the same manner as in Example-2, good images were obtained.

Comparative Example 1 Particles (A) in Example 3 (triboelectric charge amount-2 μc / g)
Images were printed in the same manner as in Example 3 using only the toner as toner, and the image density when printing 1000 sheets was 0.2.
It was as low as ~ 0.4 and had a lot of fog.

Comparative Example-2 100 parts by weight of the particles (A) of Example-5 (the triboelectrification amount is -2)
was 0.5 μc / g), 0.5 part by weight of colloidal silica treated with amino silicone oil was externally added. When an image was printed using the above-mentioned developer with a Canon copying machine NP-3525, the image density when printing 1000 sheets was as low as 0.2 to 0.4 and the fog was remarkable.

Comparative Example-3 The composition of the particles (A) of Example-5 was added to 1000 parts by weight of Example-4.
40 parts by weight of the particles (B) were added and kneaded and pulverized according to the method of Example 5 to obtain a toner of 12 μm in the same manner. The triboelectric charge amount was +2 μc / g. When external images were added and images were formed in the same manner as in Example 5, the image density was low at 0.2 to 0.4 when 1,000 images were printed, and fog was remarkable.

[Brief description of drawings]

In the accompanying drawings, FIG. 1 is a diagram schematically showing an example of a stirring device for pretreating particles (A) and particles (B), and FIG. 2-1 shows particles (A). FIG. 2 is a view schematically showing an example of an apparatus for immobilizing particles (B), FIG. 2-2 is a partially enlarged view of the apparatus of FIG. 2-1 and FIG. It is the figure which showed roughly another example of the apparatus for immobilizing particle (B) to (A), and FIG. 3-2 and FIG.
FIG. 4 is a partial view of the device of FIG. 1, and FIG. 4-1 is a diagram schematically showing an example of a pin mill system device for immobilizing particles (B) on particles (A). FIG. 2 is a partial view of the apparatus shown in FIG. 4-1, and FIG. 5 is a view schematically showing an image forming apparatus used for image formation using the toner of the present invention. 6 and 7 are enlarged views of the developing area in the apparatus of FIG. 5, and FIG. 8 is a view schematically showing a cross section of the toner of the present invention. 1 …… Jacket 2 …… Stirring blade 3 …… Motor 4 …… Lid 5 …… Base 6 …… Control plate 7 …… Cylinder 8 …… Lock of lid 9 …… Cylinder 10 …… Direction control unit 11 …… Discharge Outlet 12 …… Rotating shaft 13 …… Rotor 14 …… Dispersing blade 15 …… Rotating piece (blade) 16 …… Partitioning disk 17 …… Case sink 18 …… Liner 19 …… Impact section 20 …… Inlet chamber 21 …… Outlet chamber 22 …… Return path 23 …… Product take-out valve 24 …… Raw material input valve 25 …… Blower 26 …… Jacket 27 …… Rotating shaft 28 …… Casing 29 …… Liner 30 …… Blower vanes 31 …… Rotor ( 32) Outlet 33 ... Raw material inlet 34 ... Return path 35 ... Product outlet 36 ... Inlet 37 ... Jacket 38 ... Casing 39 ... Fixed pin 40 ... Inlet 41 ... Raw material input Mouth 42 …… Circulation blower 43 …… Return path 44 …… Product outlet 45… Outlet 46 ...... rotor 47 ...... rotary shaft 48 ...... Jiyaketsuto 61 ...... colored particles (A) 62 ...... charge control particles (B) 103 ...... photoreceptor 122 ...... sleeve 123 ...... magnets

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 63-49766 (JP, A) JP 63-138358 (JP, A) JP 63-2075 (JP, A) JP 59- 174857 (JP, A) JP 61-93603 (JP, A) JP 57-129444 (JP, A)

Claims (3)

[Claims] 1. A colored particle (A) having a softening point of 90 to 150 ° C., containing at least a binder resin and a colorant, and having a particle size ratio of 0.2 or less with respect to the colored particle (A) and having a triboelectric charge amount. Of the charge controllable resin particles (B) having a triboelectrification characteristic with an absolute value of 3 μc / g or more at a shortest interval of 0.5 to 5 mm formed from a rotating piece and a fixed piece under an atmospheric temperature of 30 to 70 ° C. The impact part or the impact part having a shortest interval of 0.5 to 5 mm formed from at least two kinds of rotating pieces is passed, and the impact part is rotated so that the peripheral speed of the tip becomes 30 to 150 m / sec. The charge controllable resin particles (B) are coated on the surface of the colored particles (A) by a mechanical impact by a rotating piece.
A method for producing a toner for developing an electrostatic charge image, characterized in that the toner is fixed at 50%. 2. The volume average particle diameter of the colored particles (A) is 2 to 20 μm.
The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein 3. The electrostatic charge image according to claim 1, wherein the charge controllable resin particles (B) have a weight ratio of the charge controllable substance to the resin of 50:50 to 1:99. Method for producing developing toner.