JPH02264266A - Production of toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain the toner having excellent durability and fixability and to obtain copied images having high image quality over a long period of time by immobilizing fine particles having a release property together with resin particles in a powder state by a mechanical impact. CONSTITUTION:The colored particles A contg. at least a binder resin and coloring agents, 0.2 to 20pts.wt. releasable particles B having <=0.2 grain size ratio to the colored particles A and 40 to 130 deg.C softening point and 1 to 30pts.wt. resin particles C having <=0.2 grain size ratio to the colored particles A are mixed. The mixture composed thereof is passed through an impact part having the shortest spacing of 0.5 to 10mm formed of a rotating piece and a stationary piece or at least two kinds of the rotating pieces under the conditions of 10 to 90 deg.C atmosphere temp. The releasable particles B and the resin particles C are simultaneously immobilized to the surfaces of the colored particles A by the mechanical impact of the impact part. The toner for heat roller fixing which has the good fixability and particularly the good offset resistance is obtd. in this way and the sharp images having no fogging are obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., and is particularly suitable for constant fixation on a heated roller. This is related to toner.

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2.297°69
Although many methods are known, as described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., they generally utilize photoconductive substances and perform various methods. forming an electrical latent image on the photoreceptor by means;
Next, the latent image is developed using toner, and after the toner image is transferred to a transfer material such as paper as necessary, it is fixed by heat, pressure, heat pressurization, solvent vapor, etc. to obtain a copy. be.

Various methods and devices have been developed for the process of fixing toner images on sheets such as paper. The most common method at present is the press-heating method using a heat roller.The press-heating method using a heat roller presses the toner image surface of the fixing sheet onto the surface of a heat roller whose surface is made of a material that has releasability to toner. Fixing is carried out by passing through the film while making contact with the film. In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so the thermal efficiency when fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in high-speed electrophotographic copying machines. However, in the above method,
Since the surface of the heat roller and the toner image contact each other under pressure in a molten state, a portion of the toner image adheres to and transfers to the surface of the fixing roller, and this transfers again to the next sheet to be fixed, causing a so-called offset phenomenon. It may stain the sheet to be fixed. One of the essential conditions for the heat roller fixing method is to prevent toner from adhering to the surface of the heat fixing roller.

In order to prevent the offset phenomenon during hot roller fixing, it has recently become common to include a release agent such as polyolefin such as polypropylene or polyethylene, or paraffin wax in the toner to prevent offset. However, in order to further improve offset resistance,
Attempts have been made to add a larger amount of the above-mentioned mold release agent or to use a mold release agent with a lower melting point, but this has sometimes been difficult as fusion may occur in the crusher or classifier.

As described in Japanese Patent Publication No. 51-23354, such an offset phenomenon tends to occur when a low molecular weight resin is used. Therefore, as described in the same publication, it may be possible to prevent the offset phenomenon by using a crosslinked resin, but the present inventors investigated and found that simply crosslinked resin It turns out that even if you create one, it is not necessarily good. If the degree of crosslinking is high, the fixing temperature will be high, which is problematic, especially in the case of magnetic toners, because the fixing temperature further increases and offset resistance deteriorates.

In addition, in order to prevent toner from adhering to the surface of the fixing roller,
The roller surface is made of a material that has excellent releasability for toner, such as silicone rubber or fluorine-based resin, and is further coated with a release agent such as silicone oil to prevent offset and roller surface fatigue. The surface of the roller is coated with a thin film of a liquid with good properties. However, although this method is extremely effective in preventing toner offset, the offset prevention liquid evaporates due to heating, giving the user an unpleasant odor, and requires a device to supply the offset prevention liquid. Therefore, there are problems such as a complicated fixing device.

Therefore, the method of preventing offset by supplying an anti-offset liquid is not preferable (although the current situation is that it is desired to develop a toner with high offset resistance that has a wide fixing temperature range. However, in addition to fixing properties, toners also need to be excellent in anti-blocking properties, developing properties, transferability, cleaning properties, etc. However, conventional toners have one or more of the following defects. That is, many toners that melt easily at relatively low temperatures when heated tend to cake or agglomerate during storage or in copiers.Many toners lose their triboelectric properties and In addition, many toners suffer from mutual deterioration of toner, carrier particles, and photosensitive plate due to collision between toner particles and carrier particles due to repeated development through continuous use and contact between them and the photosensitive plate surface. The density of the printed image changes or the background density increases, degrading the quality of the copy.Furthermore, the amount of toner adhering to the surface of the photosensitive plate with the latent image increases, increasing the density of the copy image. When this happens, the background density usually increases, causing a so-called fog phenomenon.

There is a strong demand for the development of toners that have high anti-offset properties and anti-blocking properties.

As a solution to this problem, the present applicant has proposed a method in which a releasable substance is mixed with toner base particles and an impact force is applied to the toner base particles to cause the releasable particles to adhere to the surface of the toner base particles. This method was very excellent in terms of offset resistance. However, although the releasable particles are physically implanted in the center direction on the surface of the base particle, there is no connection in the connecting direction, and as a result, they are separated due to rubbing between the carrier, sleeve, and torsion. The molding substance is likely to be detached, and blocking may occur in the developing device or during storage, and the problem has not been satisfactorily solved.

[Problems to be Solved by the Invention] An object of the present invention is to provide a toner that overcomes the above-mentioned toner defects.

That is, an object of the present invention is to provide a toner for hot roller fixing that has good fixing properties and particularly good anti-offset properties.

A further object of the present invention is to provide a toner for hot roller fixing that has good chargeability and always exhibits stable chargeability during use, and provides clear and fog-free images.

[Means and effects for solving the problems] The present invention provides colored particles A having at least a binder resin and a colorant, and particles having a particle size ratio of 0.2 or less and a softening point of 40. ~
32 to 20 parts by weight of releasable particles BO at 130°C and resin particles C1 to 3 having a particle size ratio of 0.2 or less with respect to colored particles A
0 parts by weight of the mixture is passed through an impact section formed from a rotating piece and a fixed piece or at least two types of rotating pieces and having a minimum gap of 0.5 to 10 mm at an ambient temperature of 10 to 90°C. This is a method for producing a toner for developing an electrostatic image, characterized in that releasable particles B and resin particles C are simultaneously immobilized on the surface of colored particles A by mechanical impact.

The present invention will be described in detail below.

Normally, in the case of toner obtained by kneading or pulverization, the release agent and binder resin are generally not compatible with each other, and the release agent exists unevenly in the toner particles, making it difficult to control the amount on the surface. It was difficult.

In other words, there are differences in dispersibility depending on the kneading properties of the binder resin and mold release agent used, as well as the cross-crossing method. There are concerns about poor dispersibility of the colorant, etc., and it is not necessarily the case that the preferred method of intermixing is adopted for the release agent.As a result, the way the release agent breaks due to the impact is different, and the amount of the toner surface area is It is assumed that this will change.

In addition, sometimes the release agent is liberated from the binder resin, causing carrier contamination and sleeve contamination and deteriorating the phenomenon characteristics.

In addition, a large amount of liberated mold release agent is mixed into the fine powder after classification and the fine powder in the collector, and when this fine powder is reused, it causes problems such as changes in composition and changes in performance.

The toner according to the present invention is one in which the fine particles B having mold releasability are fixed together with the resin particles C in a powder form by mechanical impact. The release agent does not become separated due to stirring during development, stirring during development, rubbing, etc. (it acts as an integral part of the toner), and the amount of the release agent on the surface of the toner is controlled and is present uniformly. As a result, it is thought that good offset properties can be obtained by uniformly and effectively melting the mold release agent on the surface under heat and pressure.Furthermore, the toner produced by this method is firmly fixed by the resin particles C. Because of this, there is little free release agent (good development characteristics can be obtained without causing carrier contamination or sleeve contamination).

In addition, in the case of toner obtained by the V turbidity polymerization method,
In general, the release agent has strong hydrophobicity, and is generally present inside the toner particles, with only a small amount present on the surface. This method has the advantage of being able to incorporate a large amount of mold release agent and the use of a low melting point mold release agent, and has good offset properties. Having a mold release agent is more preferable for offset properties. As a result, the female mold agent on the surface melts uniformly and effectively under heat and pressure, providing good offset properties.

Furthermore, such a method has the advantage that it is possible to use a mold release agent with a high melting point, which is difficult to melt and disperse in monomers in conventional suspension polymerization methods.

In addition, in the case of capsule toner whose surface is coated with a resinous material, it is difficult to coat it with a resinous material containing a release agent due to limitations in the manufacturing process, and generally the surface is coated with a resinous material that contains a release agent. No molding agent included. A controlled release agent can also be immobilized on the surface of such toner. As a result, the mold release agent on the surface melts uniformly and effectively under heat and pressure, providing good offset properties.

The releasable particles B and the resin particles C are powdered together with the colored particles A, and the releasable particles B and the resin particles C are immobilized on the colored particles A by mechanical impact.

In insulating toner, it is important to adjust the amount of triboelectric charge to a constant value. In other words, one of the important characteristics of being able to obtain good images under different environments, and being able to obtain good images that are as good as the initial image even during continuous image production, is how to control the amount of triboelectric charge. .

In general, mold release agents work to suppress the absolute amount of charge,
As a result, especially in high-temperature environments, it takes time for sufficient charging to occur, and toner that adheres to areas other than the latent image area due to forces other than electrical force cannot be removed, resulting in problems such as smearing the image. arise. These problems can be solved by partially immobilizing the releasable particles B. That is, by uniformly and partially existing the releasable substance on the colored particles A, the influence on the triboelectric charging property (based on the releasable substance) is minimized.

On the other hand, this is presumed to be due to the fact that it is difficult to avoid such an effect on triboelectrification when the releasable substance is present entirely on the particles A.

As the releasable particles B, particles in which a releasable substance is dispersed in a resin are used.

It is preferable that the value of (average particle size of release particles B/average particle size of colored particles A) of release particles B and colored particles A is 0.2 or less. When the particle size ratio exceeds 0.2, it is difficult to uniformly immobilize the releasable particles B on the surface of the colored particles A.

Particle size distribution is measured by the following measuring method. The measuring device is Coulter Counter T A-II type (manufactured by Coulter) or Elzone Verticle Counter 80XY.
-2 (manufactured by Particle Day Co., USA) to output the number average distribution and volume average distribution. Electrolyte is 1-4% Na
A Cρ aqueous solution is used.

As a measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 mR of the electrolytic aqueous solution in an amount of 0.1 to 5 mJ? In addition, 0.5 to 50 mg of the measurement sample is added.

The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and
Type or Elzone Verticle Counter 80X Y -
2, the particle size distribution of particles with a diameter of 0.2 to 40 mm is measured using a 12 to 120 aperture as an aperture, and the volume average distribution and number average distribution are determined.

Substances with mold release properties are defined by the ring and ball method (JIS K 2531).
etc.) has a softening point of 40 to 130°C, preferably 50 to 120°C. Softening point is 40
If it is less than 130°C, the blocking resistance and shape retention of the toner will be insufficient, and if it exceeds 130°C, there will be little effect in lowering the fixing temperature or fixing pressure. Preferably, the softening point is 80°C.
~120°C. Such compounds include wax,
Low molecular weight polyolefins, modified waxes having aromatic groups, hydrocarbon compounds having alicyclic groups, natural waxes, long hydrocarbon chains having 12 or more carbon atoms [C11, (-CI!2)
H, 1 or +-C112+-+2 or more aliphatic carbon chains]
long-chain carboxylic acid having esters thereof, fatty acid metal salts thereof,
Examples include fatty acid acid, fatty acid bisand, and the like. A mixture of different low softening point compounds may be used.

Specifically, microwax (manufactured by Nippon Oil Co., Ltd.), microcrystalline wax (manufactured by Nippon Seiro Co., Ltd.), PE-130 (
(manufactured by Hoechst), Mikata Hiwax 110P (manufactured by Mitsui Petrochemical), Mikata Hiwax 220P (manufactured by Mitsui Petrochemical), Mikata Hiwax 660P (manufactured by Mitsui Petrochemical),
Mikata Hiwax 210P (Mitsui Petrochemical), Mikata Hiwax 320P (Mitsui Petrochemical), Mikata Hiwax 410P (Mitsui Petrochemical), Mikata Hiwax 420P (Mitsui Petrochemical), modified wax JC-1
141 (Mitsui Petrochemical), modified wax JC-213
0 (Mitsui Petrochemical), modified wax JC-4020 (
Modified wax JC-1142 (manufactured by Mitsui Petrochemicals), modified wax JC-5020 (manufactured by Mitsui Petrochemicals): Examples include polytetrafluoroethylene such as beeswax, carnauba wax, and monk's wax.

Examples of fatty acid metal salts include zinc stearate, calcium stearate, magnesium stearate, zinc oleate, zinc palmitate, and magnesium palmitate.

One or more types of these can be used.

As the resin used for the releasable particles B, toner binding substances can be used, such as monopolymers of polystyrene and its substituted products; styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, etc. Polymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-
Styrenic copolymers such as acrylonitrile-indene copolymers Niacrylic resins, methacrylic resins, silicone resins, polyester resins, furan resins, epoxy resins,
Examples include. Preferred binding materials include crosslinked styrenic copolymers or polyesters. Examples of monomers for this styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and methacrylate. acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate,
Monocarboxylic acids or substitutes thereof having double bonds such as acrylonitrile, methacrinitrile, acrylamide, etc.; dicarboxylic acids having double bonds such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, etc. and its substituted products: As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, such as ethylene glycol divinyl compounds, etc. Carboxylic acid esters with two double bonds such as acrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and three or more vinyl Compounds having groups can be used alone or in mixtures.

The Tg of such a resin is preferably 50° C. or higher, preferably 55° C. or higher in view of so-called blocking properties during long-term storage. In particular, in the cross-wire pulverization means of the releasing substance and the resin, the particle size ratio of single particles of the releasing substance to the colored particles A is 0.
When it is 2 or more, it is an effective means because it can be made into powder by dispersing a mold-releasing substance in the resin and making it 0.2 or less.

Moreover, polymer particles can also be used as the releasable particles B.

Polymerizable monomers that can be used to form the heavy metal releasable particles B are monomers having a CIl□=C< group as a reactive group, such as styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, -methylstyrene, p-methoxystyrene,
Styrene and its derivatives such as p-ethylstyrene; 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, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. α-methylene resin group monocarboxylic acid esters; methyl acrylate, ethyl acrylate,
Acrylic acid esters such as n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate. ; There are monomers having reactive double bonds such as vinyl groups such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrinitrile, and acrylamide. These may be used alone or in combination. A crosslinking agent may be used if necessary.

As a crosslinking agent, divinylbenzene, divinylbenzene,
Examples include dielene glycol dimethacrylate and ethylene glycol dimethacrylate. The amount of crosslinking agent added is usually 0.1 to 100 parts by weight of the polymerizable monomer.
5 parts by weight are used.

Further, a small amount of a polymer of these polymerizable monomers may be added to the monomer composition. Among the monomers mentioned above, polymer particles produced from styrene, styrene having a substituent such as an alkyl group, or a mixed monomer of styrene and other monomers are considered in consideration of developability and durability. It is preferable if

The ratio of the above-mentioned mold release substance to the resin in the polymer particles is preferably 0.1 to 10%.

Furthermore, a commonly known charge control agent may also be used in combination.

The charge control material in the present invention refers to a material that satisfies the following triboelectric properties. That is, 100 parts by weight of a bulk polymer of polystyrene resin (weight average molecular weight approximately 100,000 to 200,000) was mixed with 5 parts by weight of a charge control substance using a hot roll.
The mixture is thoroughly kneaded at ~150°C (for example, 30 minutes to 1 hour), cooled, and then crushed and classified to prepare polystyrene particles containing a charge-controlling substance having a main particle size of 10p. Adjusted polystyrene particles 5g and 200~
Carrier iron powder that is not coated with resin and has a main particle size of 300 mesh (for example, Nippon Tetsuko Co., Ltd., EFV200/
After leaving 95g of 300) in an environment of 50 to 60% R11 at 25°C overnight, the mixture was thoroughly mixed in a polyethylene container with a capacity of about 200 cc for about 5 to 10 minutes)4
The amount of triboelectric charge is measured by a conventional blow-off method using an aluminum cell having a 00 mesh screen.

The triboelectric charge measured by this method is 3 in absolute value.
It has a value of pc/g or more, particularly 7 pc/g or more.

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

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

Nigrosine, azine dyes containing alkyl groups having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes [
For example, C, L Basic Yellow 2 (C:, 1.
41000), C, 1, Basic Yellow 3, C,
1, Basic Red l (C, 1,4516
0), C,1, Basic Red 9 (C,1
, 42500), C, 1, Basic Violet
1 (C, 1, 42535), C, 1, Basic Violet 3 (C, 1, 42555), C, 1, Basic Violet 10 (C, 1, 45170),
C, 1, Basic Violet 14 (C, 1, 4
2510), C,1, Basic Blue 1 (C
,1,42025),C,1,Basic Blue 3
(C, 1, 51005C, 1, Basic Blue 5 (C, 1, 42140C, 1, Basic Blue 7 (C, 1, 42595C, 1, Basic Blue 9 (C, 1, 52015C, 1, Basic Blue 24 (C ,1,52030C,1,
Basic Blue 25 (C, 1,52025C
,1,Basic Blue 26 (C,1,440
45C, 1, Basic Green 1iC, 1, 42
040C, 1, Basic Green 4 (C, 1,
42000)], lake pigments of these salt-based materials, (lake forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, etc.) (Russian compound, etc.), C, 1, Sovent Black 3
(C, 1, 26150), Hansa Yellow G (C, 1
, 11680), C, 1, Mordrant Black 1
1, C, 1, Pigment Black 1 Benzolmedylhexadecyl ammonium chloride, decyl-trimedelammonium chloride, or dialkyltin compounds such as dibutyl or dioctyl, dialkyltinborate compounds, guanidine derivatives, vinyl containing amino groups Polyamine resins such as polyester polymers and condensation polymers containing amino groups.

(2) The following substances can be used to control the negative chargeability of toner. Special Publication No. 41-20153, No. 43-275
96, No. 44-6397, and No. 45-26478. Tokuko Showa 5
No. 5-42752, No. 5g-41508, No. 58-7
Zn and Aj+ of salicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid described in No. 384 and No. 59-7385.

Metal complexes such as Co, Cr, and Fe, and sulfonated copper phthalocyanine pigments.

Furthermore, the charge control substance used in the present invention must have little environmental dependence, be thermally stable, mechanically stable, and chemically stable. .

Such releasable particles B are produced by the following method, but are not limited thereto.

In the case of a single mold release agent, it is usually obtained by known pulverization.

Preferably, freezing and pulverization is preferred because fine particles can be easily obtained.

Alternatively, it may be dissolved in a solvent at room temperature or heated and precipitated in a poor solvent, or precipitated after cooling. In this method, it is preferable to carry out the reaction with stirring, but it may be carried out without stirring.

In such a method, a dispersant may be used within a range that causes no practical problems. Furthermore, the dispersant may be removed by washing with water, acid, alkali, etc. before use. Fine particles may also be obtained by heated spraying.

When the releasable particles B are resin particles containing a releasable substance, the releasable substance and the resin are hot-melted and kneaded, cooled, and pulverized by a commonly known method to obtain fine particles. If necessary, fine particles having a preferable particle size may be obtained by classification.

Alternatively, fine particles may be generated by heating and spraying a composition of a resin and a releasing substance.

Further, polymerization is performed in the presence of a releasing substance in an organic solvent that dissolves the monomer but does not dissolve the polymer produced from the monomer, thereby producing fine polymer particles having the releasing substance,
The polymer fine particles may also be obtained by removing the solvent.

Furthermore, there is also a method of obtaining fine particles of a polymer produced from a monomer having a releasing substance by dispersing the releasing substance in the monomer and carrying out suspension polymerization in a medium that does not substantially dissolve the monomer. On this occasion,! As the dispersant used in the turbid polymerization, a dispersant such as silica or calcium phosphate is used. It is preferable to remove the dispersant from the polymer particles by washing with water or using an acid-alkali solution, but if there is no practical problem, it is not necessary to remove the dispersant from the polymer particles.

The amount of release particles B to be added to colored particles A is preferably 0.2 to 2 parts by weight when using the above-mentioned release particles themselves as release particles B, and when used together with a binder resin. When doing so, it is preferable to adjust the proportion of the particles themselves having mold releasability to 0.2 to 2 parts by weight.

As the resin used for the resin particles C, toner binding substances can be used, such as monopolymers of polystyrene and its substituted products, styrene-acrylic acid ester copolymers, and styrene-methacrylic acid ester copolymers. , styrenic copolymers such as styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, acrylic resin, methacrylic resin, silicone resin, polyester resin, Examples include furan resin and epoxy resin. Preferred binding materials include crosslinked styrenic copolymers or polyesters. Examples of the monomer of this styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
Monocarboxylic acids with double bonds such as 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Substituted products thereof: For example, dicarboxylic acids having double bonds such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, etc. and substituted products thereof: Here, as a crosslinking agent, mainly two or more polymerizable Aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, etc., such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc. are used. Divinyl compounds such as carboxylic acid ester divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone having two double bonds, and compounds having three or more vinyl groups are used alone or as a mixture.

The Tg of such a resin is preferably 50° C. or higher, preferably 55° C. or higher in view of so-called blocking properties during long-term storage.

Next, regarding the fixation method, it is preferable that the colored particles A, releasable particles B, or resin particles C be released in the toner, or that the releasable particles B or resin particles C that have been attached to the toner be released again. (, it is preferable to immobilize more reliably.

It is important to control the impact force within a range that does not crush the colored particles A and the temperature within a range that does not cause fusion and aggregation. As an example of the immobilization device for carrying out this method, a bottle mill (with a recycling function and many rotating pins) (
(see Figure 4-1), and a crusher that applies an impact between a rotating blade or hammer (rotating piece) and a liner (fixed piece) and has a recycling function (see Figure 2-1 and 3-1).
(see figure) is valid.

The circumferential speed of the tip of the rotating piece in this device is 30 to 150 m/
Sea is preferred. The ambient temperature varies depending on the physical properties of colored particles A and releasable particles B or resin particles C, but is 20 to 90°C.
, preferably from 30 to 70°C, and the residence time in the impact portion is preferably from 0.02 to 12 seconds. In the case of a bottle mill, it is necessary to increase the concentration of the powder.
In the type of apparatus shown in Figure 1, the powder to be processed is collected near the liner by centrifugal force, so the latitude of the powder concentration is wide. Good results are obtained when the shortest gap between the bottle mills or between the blade or the hammer and the liner is preferably adjusted to about 0.5 to 10 mm, more preferably 1 to 8 mm.

To explain in more detail with reference to FIG. 2-1, the colored particles A, releasable particles B, and resin particles C pretreated by the method described above are introduced through the inlet 24, pass through the inlet chamber 20, and are rotated. The blade 15 rotates along the dispersion vane 14 to
and the liner 18, passes through the outlet chamber 21, passes through the return passage 22 and the blower 25, and circulates through the same circuit again. After the immobilization process is completed, colored particles A including releasable particles B and resin particles C are taken out from the product outlet 23.

Here, the powder consisting of colored particles A, releasable particles B, and resin particles C is subjected to impact and immobilization treatment between the blade 15 and the liner 18 in the impact section 19. Here, if necessary, it is preferable to flow cooling water into the jacket 26 to adjust the ambient temperature. 2-2
In the figure, the gap a between the blade 15 and the liner 18 is the shortest gap, and the space corresponding to the width of the blade 15 is the impact portion.

FIG. 3-3 shows the positional relationship between the liner 29 of the immobilization device and the rotating rotor 31, and the shortest gap between the liner 29 and the rotor 31 is defined as the tip of the protrusion toward the inner periphery of the liner 29. This refers to the difference in the radius of two circles, the circumference 51 obtained by connecting the two circles, and the locus 52 of the protrusion 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 bottles in the bottle milk immobilization device when viewed from the front of the device, and the gap 55 between the fixed bottle 39 and the rotating bottle 54 is the shortest gap. In addition, 15
indicates the maximum gap, and 56 indicates the locus of the rotating pin 54.

Colored particles A can be obtained, for example, as follows. The colored particles A produced by the pulverization method include at least a binder resin, a colorant,
A mixture consisting of a mold release agent, if necessary, is melt-kneaded, cooled, and then pulverized using a commonly known pulverizer, and if necessary, classified to have a uniform particle size distribution. The volume average particle size of the colored particles A preferred as a developing toner is 2 to 20 μm.

Examples of binder substances for toner include monopolymers of polystyrene and its substituted products; styrene-acrylic ester copolymers, styrene-methacrylic ester copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers. Polymers, styrenic copolymers such as styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; acrylic resins, methacrylic resins, silicone resins, polyester resins, epoxy resins, etc. can be used. Preferred binding materials include crosslinked styrenic copolymers or polyester resins. Examples of monomers for this styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, Monocarboxylic acids having double bonds such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. or substituted products thereof, such as maleic acid, butyl maleate, maleic acid, etc. Vinyl monomers such as dicarboxylic acids having double bonds such as methyl acid and dimethyl maleate, and substituted products thereof; may be used alone or in combination of two or more.

As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as aromatic divinyl compounds such as divinylbenzene and divinyl sulfone, such as ethylene glycol diacrylate and ethylene glycol diacrylate. Divinyl compounds such as carboxylic acid ester divinylaniline having two double bonds, divinyl ether, divinyl sulfide, divinyl sulfone, etc., such as methacrylate, 1,3-butanediol dimethacrylate, etc., and compounds having 3 or more vinyl groups. Used alone or in mixtures.

Next, the colorant used in the colored particles A produced by the pulverization method will be described. To produce magnetic toner, magnetic particles are added. In this case, the magnetic particles also serve as a coloring agent. The magnetic particles that can be used in the present invention include substances that are magnetized when placed in a magnetic field, such as powders of ferromagnetic metals such as iron, cobalt, and nickel, or powders of alloys and compounds such as magnetite and ferrite. can be mentioned. Particle size is 0.1~II'', preferably 0.1~0.5
)i.

Magnetic particles are used. The content of the magnetic particles is 10 to 65% by weight, preferably 20% by weight, based on the weight of the toner.
~60% by weight is good. Further, these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent or a titanium coupling agent, or an appropriate reactive resin. In this case, it depends on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, but it is 5% by weight or less (preferably 0.1 to 3% by weight)
Sufficiently preferable dispersibility can be obtained with a treatment amount of .

The colored particles A produced by the polymerization method can be obtained, for example, by the method shown below, but are not limited thereto. A monomer system in which polymerizable monomers, colorants, polymerization initiators, crosslinking agents, charge control agents, polar polymers, and other additives are uniformly dissolved or dispersed is added to an aqueous phase containing a suspension stabilizer ( (that is, a continuous phase) and granulation polymerization is carried out under stirring.

Thereafter, the suspension stabilizer is removed, separated and dried.

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

Polymerizable monomers that can be used to form polymerized colored particles A are monomers having a C1 (2.C〈 group as a reactive group, such as styrene, 0-methylstyrene, m-methylstyrene, p- Methylstyrene, p-methoxystyrene, p
- Styrene and its derivatives such as ethylstyrene Niacrylic 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,
α-methylene aliphatic monocarboxylic acid esters such as stearyl methacrylate, phenyl methacrylate, dimethylaminoedyl methacrylate, diethylaminoedyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate , propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and other acrylic acid esters; acrylonitrile,
There are monomers having reactive double bonds such as vinyl groups such as acrylic acid or meccrylic acid derivatives such as tolyl methacrylate and acrylamide. These may be used alone or in combination. A crosslinking agent may be used if necessary. As a crosslinking agent, divinylbenzene, divinylnaphthalene, diethylene glycol dimethacrylate,
Examples include ethylene glycol dimethacrylate.

The amount of the crosslinking agent added is usually 0.1 to 5 parts by weight per 100 parts by weight of the polymerizable monomer. Further, a small amount of a polymer of these polymerizable monomers may be added to 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 other monomers have excellent developability and durability. This is preferable when considering the following.

Further, a preferable polymerized toner can be obtained by adding a polar polymer, a polar copolymer, or a cyclized rubber having a polar group as an additive during polymerization of the monomer to polymerize the polymerizable monomer. The polar polymer, polar copolymer or cyclized rubber is preferably added in an amount of 0.5 to 50 parts by weight, preferably 1 to 40 parts by weight, per 100 parts by weight of the polymerizable monomer. If it is less than 0.5 parts by weight, it is difficult to obtain a sufficient pseudocapsule structure, and if it is more than 50 parts by weight, the amount of polymerizable monomer is insufficient and the properties as a polymerized toner tend to deteriorate. A polymerizable monomer composition containing a polar polymer, a polar copolymer, or a cyclized rubber is suspended in an aqueous phase of an aqueous medium in which a dispersant having an opposite charge to the polar polymer is dispersed, and polymerization is carried out. That is, the cationic or anionic polymer, cationic or anionic copolymer, or anionic cyclized rubber contained in the polymerizable monomer composition is preferably dispersed in an aqueous medium. The oppositely charged anionic or cationic dispersant is electrostatically attracted to the surface of the toner particles, and the dispersant covers the particle surface to prevent the particles from coalescing and stabilize them, as well as the added polar polymer. , because the polar copolymer or cyclized rubber gathers on the surface layer of the particles that become the toner.
It takes on a kind of shell-like form, and the resulting particles become pseudo-capsules.

Since the relatively high molecular weight polar polymer, polar copolymer, or cyclized rubber gathered on the surface layer of the particles encapsulates a large amount of low softening point compounds inside the toner particles, the polymer particles of the present invention have blocking properties. Provides excellent developability and abrasion resistance. Examples of polar polymers (including polar copolymers and cyclized rubbers) and counterloadable dispersants that can be used in the present invention are shown below. Incidentally, polar polymers having a weight average molecular weight of 5.000 to 500.000 as measured by GPC are preferably used because they dissolve well in the polymerizable monomer and have durability.

(i) Examples of the cationic polymer include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl acrylate, copolymers of styrene and the nitrogen-containing monomers, styrene, unsaturated carboxylic acid esters, etc. There is also a copolymer of the nitrogen-containing monomer and the nitrogen-containing monomer.

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

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

(City) As an anionic dispersant, Aerosil #200
．． There are colloidal silicas such as #300 (manufactured by Nippon Aerosil Co., Ltd.).

(iv) Aluminum oxide as a cationic dispersant;
Examples include magnesium hydroxide and hydrophilic positively charged silica fine powder such as aminoalkyl-modified colloidal silica treated with a coupling agent.

An anionic cyclized rubber may be used instead of the above-mentioned polar polymer or copolymer.

To produce the magnetically polymerized colored particles A, magnetic particles are added to the monomer composition. In this case, the magnetic particles also serve as a coloring agent. Magnetic particles that can be used in the present invention include:
A substance that is magnetized when placed in a magnetic field is used, such as powders of ferromagnetic metals such as iron, cobalt, and nickel, or powders of alloys and compounds such as magnetite and ferrite. The particle size is 0.05 to 5, preferably 0.05.
Magnetic fine particles having a diameter of 1 to 1 micron are used. The content of the magnetic particles is preferably 10 to 60% by weight, preferably 20 to 50% by weight, based on the weight of the toner. Further, these magnetic fine particles may be treated with a treatment agent such as a silane coupling agent or a titanium coupling agent, or an appropriate reactive resin. In this case, it depends on the surface area of the magnetic fine particles and the density of hydroxyl groups present on the surface, but it is not more than 5% by weight (preferably 0.1 to 0.1% by weight).
A treatment amount of 3% by weight) provides sufficient dispersibility in the polymerizable monomer and low softening point compound, and does not adversely affect the physical properties of the colored particles A. The colored particles A contain 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 carbon black is coated with a resin can be used. .

The colorant should be 0.000% based on the polymer and low softening point compound.
It is contained in an amount of 5 to 30% by weight. A charge control agent and a fluidity modifier may be added (internally added) to the toner as necessary.

In the suspension polymerization method, a monomer composition in which a colorant or additives added as necessary are uniformly dissolved and dispersed is
In an aqueous medium (e.g. heated to a temperature of 5° C. or higher, preferably 10 to 30° C. or higher than the polymerization temperature) containing ~50% by weight of a suspension stabilizer (e.g., a poorly soluble inorganic dispersant). Disperse using a conventional stirrer, homomixer, homogenizer, etc. Preferably, the agitation speed and time are adjusted such that the particles of the melted or softened monomer composition have the desired toner particle size, generally a size of 30 particles or less (e.g., a volume average particle size of 0.1 to 20 particles). and adjusting the temperature of the aqueous medium. Thereafter, the temperature of the aqueous medium is lowered to the polymerization temperature while stirring is performed to the extent that sedimentation of the particles is prevented, so that this state is substantially 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 a substantially water-insoluble polymerization initiator is added while stirring to carry out the polymerization. After the reaction is completed, 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 colored particles A that can be used in the present invention. In the suspension polymerization method, 200 to 3000 parts by weight of water is usually used as an aqueous dispersion medium per 100 parts by weight of the polymerizable monomer and low softening point compound.

Furthermore, it is also possible to form fine particles in the molten state after heating and mixing. Various conventionally known liquid atomization methods can be applied.

That is, a single-fluid nozzle using pressure, a two-fluid nozzle using high-pressure air flow, a disk atomizer using a rotating disk, etc. may be used.

When the fixing method of the binder resin of the colored particles A used in the present invention is heat fixing, the softening point measured by the following method is preferably 90 to 150°C, particularly preferably 90 to 140°C.

Using a flow tester CFT-500 model (manufactured by Shimabara Seisakusho), the sample was approximately 1.0 to 1.5 g of a 60-mesh bath product.
The mixture is weighed and pressurized for 1 minute using a molding machine under a load of look kg/cm2. This pressurized sample is measured with a flow tester under the following conditions, and the temperature corresponding to the stroke difference of 172 between the start of outflow and the end of outflow is defined as the softening point.

4-legged ox RATE TEMP 5. OD/M (”
C/ 1 minute) SET TEMP 50. O.D.
EG (”C)MAX TEMP 200
．． ODEGINTERVAL 2.5D
EGPRεIIEAT 300. OSEC(
seconds) LOAD 50.0 KGF
(kg) DIE (DIA) 0.5 MM
(mm) DIE (LENG) 1. O
MMP LUNGER1, OCM" (cm2) can be used. It is also possible to atomize the liquid in the molten state after heating and mixing. Various conventional methods of atomizing liquid can be applied. Namely, single-fluid nozzle using pressure, high temperature A two-fluid nozzle using airflow, a disk atomizer using a rotating disk, etc. may also be used.Also, heating and melting in a solvent,
It is also good to cool it and make it into fine particles. Here, it is also possible to use a dispersant while stirring. If necessary, it is preferable to remove the dispersant by washing with water, acid or alkali. Such a granulation method is preferred because it yields spherical particles.

Examples of capsule wall-forming substances 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-methacrylate ester Copolymers (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-acrylonitrile-acrylic ester copolymer Styrenic resins such as polymers (unipolymers or copolymers containing styrene or styrene substitutes); rosin-modified maleic acid resins, epoxy resins, polyester resins, ionomer resins, ketone resins, xylene resins, etc.

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

When uniformly immobilizing the releasable particles B and resin particles C on the colored particles A, it is preferable that the colored particles A are spherical particles with few protrusions. Preferred for immobilization.

The toner obtained by the production method of the present invention can be applied to a known dry electrostatic image development method. For example, two-component development methods such as cascade method, magnetic brush method, microtoning method, and two-component C bias development method; using magnetic toners such as conductive component development method, insulating component development method, and jumping development method. - component development method; powder cloud method and fur brush method; non-magnetic component development method in which toner is held on a toner carrier by electrostatic force to be transported to a developing section and subjected to development; electric field It is applicable to an electric field curtain development method in which toner is transported to a developing section and subjected to development using a curtain method.

[Example] The contents will be explained in detail below based on examples.

Note that all parts below are parts by weight.

Example 1 Colored particles A Styrene monomer 183 parts The above formulation was heated to 70°C and uniformly dispersed, and then the initiator [V
-601 (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd.)] was added to prepare a monomer composition.

After uniformly dispersing 0.25 parts of a silane coupling agent [KBE903 (manufactured by Shin-Etsu Silicone)] in 1200 mj of ion-exchanged water that was separately heated to 70°C, 5 g of colloidal silica [Aerosil '200 (manufactured by Nippon Aerosil)] was added. I (Cj! and P
H=6 was adjusted to form a dispersion medium system.

The above monomer composition was added to this dispersion medium system, and the monomer droplets were granulated by stirring at 7,500 rpm for 60 minutes in a TK homomixer under a nitrogen atmosphere.
Polymerization was completed in 0 hours. Thereafter, silica as a dispersant was removed by alkali treatment, and colored particles A were produced by filtration, washing with water, and drying.

When the particle size of colored particles A was measured with a Coulter counter (aperture diameter 100 p-), the volume average diameter was 10.
It was for 0.

Release Particles B The above mixture was kneaded in a roll mill at 120° C., cooled, and coarsely ground in a speed mill, then finely ground in a jet mill, and then in an air classifier to obtain particles having a volume average diameter of 1. The rate for 2 or more finishes was less than 5%.

Resin particles C were prepared by the following method, and ion-exchanged water 1ρ and 1.5
g of sodium lauryl sulfate was added, and the pH was adjusted to 1O by adding an acidic sodium carbonate solution in advance. 200 mp of styrene monomer was added to this system and vigorously stirred with a homomixer to emulsify. Introduce nitrogen gas into the system l j)/m
After the contents were heated to 75°C while the temperature was kept constant, 1 g of potassium persulfate was added to start the polymerization reaction, and the reaction was continued for about 3 hours, and then the internal temperature was increased to 80°C. The mixture was heated for 1 hour to complete polymerization. The obtained latex was purified by dialysis and treatment with an ion exchange resin to remove active agents and oligomers. The iris-emitting latex after the treatment was dried using a spray dryer to obtain spherical polystyrene particles C having a volume average particle system of 0.3H.

Next, 100 parts of colored particles A, 100 parts of releasable particles B,
60 parts of resin particles C were treated for 2 minutes using the apparatus shown in FIG. 1 at a circumferential speed of a rotating piece of 30 m/sec.

Thereafter, using the apparatus shown in FIG. 2-1, processing was carried out for 3 minutes (residence time in the impact section was 2 seconds) at a minimum gap of 1 mm and a circumferential speed of the rotating piece of 60 m/sec. Iron powder for processed toner (200
/300 mesh), the amount of triboelectric charge (triboelectric value) was -20.5 μc/g.

O and g parts of colloidal silica (Talanox 500 (manufactured by Talco)) were externally added to 100 parts of the above toner, and 94 parts of acrylic coated ferrite carrier was mixed with 6 parts of this externally added toner to prepare a developer.

When this was subjected to an image reproduction test using Canon CLC-1, a stable image was obtained up to 20,000 sheets, and although no release oil was applied to the fixing roller, no offset phenomenon was observed, and the fixing performance was affected. It was excellent.

Example 2 - Colored Particles A The above formulation was added to 70°C and dispersed using an ultrasonic disperser (RUS-300 manufactured by Nippon Seiki) at a frequency of 20KII2 and an output of 30W for 15 minutes to perform hydrophobization treatment of carbon black.

Add 4 parts of a metal complex of di-tert-butylsalicylic acid to the above treatment solution, and dissolve or disperse it uniformly while heating it to 70°C. Then add 110 parts of an initiator [V-601 (manufactured by Wako Tsumugi Co., Ltd.)]. body composition.

Colored particles A were then produced by adjusting the dispersion medium system, granulating and polymerizing in the same manner as in Example 1. The particle size of colored particles A was a volume average diameter of 9.8 m.

- Release Particles B As release particles B, three-piece Hiwax 200P was cooled and then finely pulverized with a jet mill.

(Volume average system 1 end) ・Resin particles C Resin particles C were produced in the same manner as in Example 1.

Next, 1000 parts of colored particles A, 830 parts of releasable particles, and 60 parts of resin particles C were added to 1000 parts of colored particles A, using the apparatus shown in FIG.
Processing was performed at 0 m/sec for 2 minutes.

Thereafter, using the apparatus shown in FIG. 2-1, processing was performed for 3 minutes (residence time in the impact section was 2 seconds) with a minimum gap of 1 mm and a circumferential speed of the rotating piece of 60 m/sec. Iron powder for processed toner (200
/300 mesh), the amount of triboelectric charge (triboelectric value) was -19.0 gc/g.

100 parts of the above toner were mixed with colloidal silica (Talanox 500 (manufactured by Talco)) in o and g parts, and 6 parts of this externally added toner was mixed with 94 parts of acrylic coated ferrite carrier to prepare a developer.

When this was subjected to an image reproduction test using Canon NP-4835, a stable image was obtained up to 10,000 copies, and there was no offset (the fixability was also excellent).

Example 3 - Colored particles A: C,1, Pigment Blue 15 as a coloring agent to 100 parts by weight of a polyester resin obtained by condensing a propylene oxide adduct of bisphenol A and fumaric acid.
After premixing in a Henschel mixer, melting and cross-mixing in a three-roll mill, pulverization in a jet mill, and further classification, colored particles Δ having an average particle size of 11.5 μm were obtained.

- Release Particles B The above polymerizable monomer composition was heated to 130°C, cooled while stirring, and kept at 60°C.

A polymerizable monomer composition in which Hiwax 200P was dispersed in the form of fine particles was obtained. A monomer composition was prepared by adding 3 parts by weight of 2.2'-azobis-(2,4-dimethylvaleronitrile).

12 parts by weight of amino-modified silica (100 parts of Aerosil #200 manufactured by Aerosil Co., Ltd. treated with 5 parts by weight of aminopropyltriethoxysilane) and 600 parts by weight of distilled water,
The prepared monomer composition was added to a stainless steel container with a capacity of 2ρ containing 30 parts by weight of 1/ION hydrochloric acid, and heated at 60°C.
10.0 using TK homo mixer (manufactured by Tokushu Kika Kogyo)
A dispersion liquid was prepared by stirring at 00 rpm for 60 minutes for preliminary dispersion. This dispersion liquid was discharged using a piston-type high-pressure homogenizer (manufactured by Gorlin, model 15M-87A) at a discharge pressure of 40
The pellets were granulated at a rate of 0 Kg/cm''. The time required for granulation was 5 minutes. After granulation, the mixture was stirred at 60°C for 10 hours using a paddle stirring blade to complete the polymerization.

Particles were then obtained by cooling, washing with sodium hydroxide solution, dehydration, and drying.

Tg was 90°C. The obtained particles have a volume average diameter of 1.
It was 2μ.

-Resin particles C Using the same polyester resin as colored particles A, jet milling was repeated under cooling and further classification to obtain resin particles C having an average particle size of 0.2μ.

Next, 10 parts of releasable particles B to 1000 parts of colored particles A.
0 parts and 0,200 parts of resin particles were treated for 2 minutes at a circumferential speed of a rotating piece of 30 m/sec using the apparatus shown in FIG.

Thereafter, using the apparatus shown in FIG. 2-1, processing was carried out for 3 minutes (residence time in the impact section was 2 sec) with a minimum gap of 1 mm and a circumferential speed of the rotating piece of 60 m/sec. Iron powder for processed toner (200/
The amount of triboelectric charge (triboelectric value) for 300 meshes is -
It was 18,5hc7g. 100 parts of the above toner plus colloidal silica [Taranox 500 (manufactured by Talco)]
00.8 parts were removed, and 94 parts of acrylic coated ferrite carrier was mixed with 6 parts of this externally added toner to prepare a developer.

When this was subjected to an image reproduction test using a Canon CLC-1, stable images were obtained up to 20,000 sheets, and there was no offset and the fixing properties were excellent.

Comparative Example A toner was obtained by carrying out the fixation treatment in Example 1 except for the resin particles C. The developer was prepared in the same manner as in Example 1 and an image output test was conducted, but the developer caused blocking in the developing device, deteriorating the charging characteristics and causing a lot of fog.

[Effects of the Invention] As described above, according to the present invention, a toner with excellent durability and fixing properties can be obtained, and high-quality copied images can be provided for a long period of time.

[Brief explanation of drawings]

In the attached drawings, Figure 1 shows particles (A) and particles (B),
FIG. 2-1 is a diagram schematically showing an example of a stirring device for pretreatment, and FIG. 2-1 is a diagram schematically showing an example of a device for immobilizing particles (B) on particles (A). And the second -
Figure 2 is a partially enlarged view of the device in Figure 2-1, and Figure 3-1 is a partial enlarged view of the device in Figure 2-1.
The figure is a diagram schematically showing an example of an apparatus for immobilizing particles (B) on particles (A), and FIGS. 3-2 and 3-
Figure 3 is a partial diagram of the apparatus shown in Figure 3-1, and Figure 4-1 is a diagram schematically showing an example of a bottle mill type apparatus for immobilizing particles (B) on particles (A). FIG. 4-2 is a diagram showing a partial view of the apparatus shown in FIG. 4-1. ■... Jacket 2... Stirring blade 3... Motor 4... Lid 5... Base 6... Control plate 7... Silling 8... Lid lock 9... Cylinder 10 ... Direction control unit 11 ... Discharge port 12 ... Rotating shaft 13 ... Rotor 14 ... Dispersion vane 15 ... Rotating piece (blade) 16 ... Partition disk 17 ... Casing 18... Liner 19... Impact part 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 ... Blowing vanes 31 ... Rotor (with blades) 32 ... Outlet 33 ... Raw material input port 34 ...・Return path 35...Product outlet 36...Inlet 37...Jacket 38...Casing 39...Fixing pin 40...Inlet 41...Raw material input port 42...Circulation blower 43... Return path 44... Product extraction port 45... Outlet 46... Rotor 47... Rotating shaft 48... Jacket

Claims (1)

[Claims] (1) Colored particles 1 consisting of at least a binder resin and a colorant
00 parts by weight, releasable particles B0.2 to 20 with a particle size ratio of 0.2 or less and a softening point of 40 to 130°C to the colored particles A
parts by weight and 1 to 30 parts by weight of resin particles having a particle size ratio of 0.2 or less to colored particles A at an ambient temperature of 10 to 9.
The surface of the colored particles A is reduced by mechanical impact in the impact part by passing through an impact part formed by a rotating piece and a fixed piece or at least two types of rotating pieces and having a minimum gap of 0.5 to 10 mm under the condition of 0°C. A method for producing a toner for developing an electrostatic image, comprising simultaneously immobilizing releasable particles B and resin particles C.