JPS6410826B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an electrostatic image developing toner for heat roller fixation for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, or the like. Generally, an electrostatic charge image is developed with toner, which is a colored powder, to form a toner image, and this toner image is fixed as it is or after being transferred to a transfer paper or the like. Among various known methods for fixing this toner image, the heat fixing method is practical in many respects, and in particular, the contact heat fixing method using a heated roller fixing device has high thermal efficiency and uses a relatively low-temperature heat source. It is widely prized because it can be used for various purposes and fixation can be achieved at high speed. However, in the contact heating fixing method, fixing is performed by the surface of a heating body such as a heating roller coming into contact with the toner and melting it, so that molten toner or semi-molten toner does not adhere to the surface of the heating body. The so-called offset phenomenon in which the image is transferred onto a subsequent transfer paper or the like is likely to occur. This offset phenomenon occurs when the viscoelasticity of the toner melted by heating is inappropriate and too small. As a means to prevent such an offset phenomenon through the properties of the toner itself, it is effective to include a polyolefin having a relatively small weight average molecular weight in the toner, and to crosslink the polymer that is a constituent component of the toner. It is known that it is effective to widen the molecular weight distribution. Conventionally, toners for developing electrostatic images are manufactured by melt-kneading a polymer, a colorant, etc., and then finely pulverizing the resulting colorant-dispersed polymer. Melt-kneading with a polymer cannot be carried out satisfactorily due to poor compatibility between the two, and this problem is particularly serious when the polymer is crosslinked. Therefore, in order to obtain effective non-offset properties, it is necessary to use an excessive amount of low molecular weight polyolefin, but since the toner becomes highly sticky, both of them adhere to the carrier, which is a component of the developer, resulting in its properties. and also stain the electrostatic image support. Also, as mentioned above, a melt-kneading step is included, but if the polymer is a crosslinked polymer, a large shearing force must be applied during melt-kneading, and this shearing force causes the molecular chains of the crosslinked polymer to break down. The effect of using cross-linked polymers is diminished as
Moreover, even if a homogeneous colorant-dispersed polymer is obtained,
Since the polymer is a crosslinked polymer, it is naturally quite tough and very difficult to grind into fine particles of the particle size required for toner (usually in the range of 1 to 50 microns). . That is, it is difficult to produce a toner with high non-offset properties by a method including melt-kneading and pulverization steps as described above. Moreover, the particle size distribution of the fine powder obtained by this manufacturing method is very wide, and in order to obtain a toner that can be used for practical purposes, it must be further subjected to a classification process, resulting in a complicated and costly process. The method itself also has the drawback of being expensive. On the other hand, as a method for directly obtaining polymer fine particles without a pulverization step, there is a method in which a polymerizable monomer is dispersed and suspended in water and suspension polymerization is performed. In this method, the polymerizable monomer is made into fine particles by stirring, and the fine particles are directly polymerized. However, it is important to prevent the fine particles from coalescing and to stabilize their dispersion and suspension. Dispersants are used for this purpose. Generally used dispersants are broadly divided into water-soluble polymers and poorly soluble inorganic compound fine powders.The former includes gelatin, starch, polyvinyl alcohol, etc., and the latter includes sulfuric acid. These include hardly soluble salts such as barium, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, and calcium phosphate, inorganic polymer substances such as talc, clay, silicic acid, and diatomaceous earth, and fine powders of metal oxides. However, even if such a dispersant as described above is present in the suspension polymerization system, it is extremely difficult to maintain the fine particles of the polymerizable monomer in a stable dispersion state until the polymerization is completed. As the polymerization progresses, the viscosity of the fine particles increases, and the coalescence of the fine particles due to their adhesive force cannot be prevented even under stirring, and as a result, the particle size of the resulting polymer increases, making it desirable as a toner. It is not possible to obtain polymer particles of particle size. The above-mentioned dispersant is used as an auxiliary agent with glycol, glycerin, etc. to increase the viscosity of the medium and prevent coalescence of the fine particles, and with electrolytes such as sodium chloride, sodium sulfate, etc. to increase the interfacial tension between water and the fine particles. A method of adding it to the system is also known, but the desired effect cannot be obtained. The present invention has been made based on the above circumstances, and an object of the present invention is to provide crosslinked polymer particles containing a low molecular weight polyolefin and a colorant, thereby providing excellent non-offset properties. In addition to having good fluidity and storage stability,
Therefore, it is an object of the present invention to provide a method for producing a toner for developing an electrostatic image to be fixed by a hot roller, which always has excellent developing characteristics and fixing characteristics. Another object of the present invention is to comprise essentially spherical crosslinked polymer particles uniformly containing a colorant, further containing a low molecular weight polyolefin, and having a particle size within the preferred range of 1 to 50 microns for a toner. The present invention provides a method for producing an electrostatic image developing toner for thermal roller fixing. Another object of the present invention is to provide a method by which a toner for developing electrostatic images for hot roller fixing, which is made of a crosslinked polymer containing a low molecular weight polyolefin, can be produced very easily. Another object of the present invention is to directly produce a toner for developing an electrostatic image for hot roller fixing, which is made of a crosslinked polymer containing a low molecular weight polyolefin having a desired particle size, without a pulverization process. This is to provide a method that can be used. In order to achieve the above object, the present invention uses a polymerizable monomer, a crosslinking agent for the polymerizable monomer, and a softening point composed of polyethylene, polypropylene, or ethylene-propylene copolymer.
A polymerization composition comprising a low molecular weight polyolefin having a temperature of 100 to 180°C, an ionic substance, and a colorant, the dispersed particles of which are charged to one polarity when dispersed in water; and an inorganic dispersant charged to the other polarity are dispersed and suspended in water, and the polymerizable monomer is polymerized and crosslinked to form a crosslinked polymer containing fine particles of low molecular weight polyolefin. A toner for developing an electrostatic image to be fixed on a hot roller, which is made of spherical particles, is obtained. To explain the manufacturing method according to the present invention in detail, first, a composition for polymerization is prepared, the dispersed particles of which are charged with either positive or negative polarity when dispersed in water. This polymerization composition is a mixture containing a polymerizable monomer, a crosslinking agent for the polymerizable monomer, a specific low molecular weight polyolefin, and a colorant,
Chargeability in water can be obtained by incorporating an ionic substance into the polymerization composition. In addition, a polymerization initiator and a charge control agent for the polymerizable monomer can be added to the polymerization composition as necessary, and further, when a one-component magnetic toner is finally obtained. , magnetic powder is added. This polymerization composition is poured into water together with an inorganic dispersant that is charged to the other polarity opposite to the dispersed particles of the polymerization composition when dispersed in water, and is dispersed and suspended by stirring. While continuing or after stirring, the system is placed under conditions where the polymerizable monomer polymerizes, and the polymerizable monomer is polymerized and crosslinked, thereby containing a specific low molecular weight polyolefin. A toner for developing an electrostatic image fixed by a hot roller made of a crosslinked polymer is produced. In the above, the dispersion and suspension system may be stirred using a homomixer, a homogenizer, etc., and the rotational speed thereof is usually 1000 to 6000 rpm. Although the polymerization temperature is 55 to 120°C, the polymerization can proceed more uniformly at a lower temperature. Examples of the polymerizable monomer that can be used in the present invention include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
α-methylstyrene, p-ethylstyrene, 2,
4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n
-nonylstyrene, p-n-decylstyrene, p
Preferred examples include styrene monomers such as -n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene. In addition, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, and vinyl benzoate. ,
Vinyl esters such as vinyl butyrate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid 2
- Chlorethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate α-methylene aliphatic monocarboxylic acid esters such as aminoethyl and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc. Vinyl ethers; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; vinylnaphthalenes, Others can be mentioned. These monomers can be used alone or in combination, or can be polymerized to form a copolymer. The crosslinking agent used in the present invention is mainly a compound having two or more polymerizable double bonds, such as aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene, and their derivatives;
For example, diethylene glycol acrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethylene Diethylenic carboxylic acid esters such as glycol dimethacrylate and tetramethylolmethane tetraacrylate, all divinyl compounds such as N,N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and those containing 3 or more vinyl groups. These compounds can be used alone or in combination. The ratio of these crosslinking agents to the polymerizable monomer is from 0.005 to
20% by weight, preferably in the range of 0.1-5% by weight. In the present invention, the low molecular weight polyolefin used is a low molecular weight polyethylene, a low molecular weight polypropylene, or a low molecular weight ethylene-propylene copolymer having a softening point of 100 to 180°C. Such low molecular weight polyolefins have, for example, a weight average molecular weight of about 1,000 to 45,000, particularly about 2,000 to 45,000.
6,000, and those made of low molecular weight polyolefin with a softening point of 130 to 160°C, and polypropylene are particularly preferred. Note that if a low molecular weight polyolefin with a softening point of less than 100°C is used, the softening point of the resulting toner will be lowered, and toner particles will tend to aggregate, and when the toner is applied to electrophotography, it will cause damage to the photoreceptor or carrier. contamination becomes significant, while the softening point
If the temperature exceeds 180°C, the softening point of the resulting toner will be too high, making it impossible to effectively obtain the offset prevention effect. The above-mentioned specific low molecular weight polyolefin as an anti-offset agent can be used as a monomer 100
1 to 20 parts by weight, preferably 3 to 15 parts by weight
Used in parts by weight. If this proportion is less than 1 part by weight, the offset prevention effect will be insufficient or uncertain, and if it exceeds 20 parts by weight, gelation will easily occur during the polymerization reaction and the polymerization will become unstable. In the present invention, fatty acid metal salts such as zinc, barium, lead, cobalt, calcium and magnesium salts of stearic acid, zinc, manganese, iron and lead salts of oleic acid, and palmitic acid are used. higher fatty acids with 17 or more carbon atoms, such as zinc salts, cobalt salts, magnesium salts,
Similarly, higher alcohols, esters of polyhydric alcohols, natural or synthetic paraffins, fatty acid esters or partially saponified products thereof, alkylene bis fatty acid amides such as ethylene bis stearoyl amide, and other substances effective in preventing offset. , can be used in combination with the above-mentioned low molecular weight polyolefin. In the present invention, as the ionic substance that charges the dispersed particles of the polymerization composition to one polarity when dispersed in water, it is preferable to use those selected from the following cationic substances and anionic substances. can. A Cationic substance (1) Cationic polymerizable monomer Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, 2-hydroxy-3-acryloxypropyltrimethylammonium chloride, 2-hydroxy -3-methacryloxypropyltrimethylammonium chloride, acrylamide, diacetone acrylamide, N-
n-butoxyacrylamide, N-vinylcarbazole, vinylpyridine, 2-vinylimidazole, and other nitrogen-containing polymerizable monomers. (2) Poorly water-soluble organic amines Aliphatic primary amines: e.g. heptylamine,
7 carbon atoms such as octylamine and dodecylamine
The above aliphatic primary amines; Aliphatic secondary amines such as dipropylamine, diisopropylamine, dibutylamine,
Boiling point of diamylamine, didodecylamine, etc. 80
Aliphatic secondary amines above ℃ Aliphatic tertiary amines: e.g. triethylamine, tripropylamine, tributylamine,
Boiling points of triamylamine, n-dodecyldimethylamine, n-tetradecyldimethylamine, etc.
Aliphatic tertiary amines above 80℃ Aromatic amines: aniline, methylaniline,
Aromatic amines such as dimethylaniline, ethylaniline, diethylaniline, toluidine, dibenzylamine, tribenzylamine, diphenylamine, triphenylamine, naphthylamine, etc. However, aliphatic amines are used in the form of an acidic aqueous solution. B Anionic substance Anionic polymerizable monomer 2-acrylamide-2-methylpropanesulfonic acid, N-methylolacrylamide, methacrylic acid, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxy methacrylate Propyl, glycidyl methacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethacrylate, tetrahydrofurfuryl methacrylate, acid phosphooxyethyl methacrylate, and other anionic polymerizable monomers. However, the above ionic substances must be able to coexist in the polymerizable monomer particles dispersed in water, and for this reason water-soluble organic amines cannot be used. However, even if ionic polymerizable monomers are water-soluble, they become part of the polymer particles by copolymerizing as the polymerization progresses, so they do not migrate to the aqueous phase and can be used. . These ionic substances may be contained in the polymerization composition in an amount of 0.1% by weight or more based on the polymerizable monomer, preferably 0.2% by weight.
That's all. There is no need to set an upper limit, but 5
Even when the content is greater than % by weight, no further effect on polymerization stability or finer particle size is observed, but such use is not prohibited. As the coloring agent used in the present invention, any suitable pigment or dye can be used, such as carbon black, nigrosine dye (Cl No.
50415B), Aniline Blue (CINo. 50405), Calco Oil Blue (CI No. azoec Blue 3), Chrome Yellow (CI No. 14090), Ultramarine Blue (CI No. 77103), DuPont Oil Red (CI
No. 26105), Orient Oil Red #330 (CI No.
60505), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo.42000), Lampblack (CINo.77266), Rose Bengal (CINo. 45435),
Oil black, azo oil black, and others can be used alone or in combination. These colorants may be contained in a proportion such that the toner as a final product contains about 3 to 20% by weight. Further, in the case where a magnetic powder described below is contained, this magnetic powder can be used as a coloring agent. In the present invention, as the polymerization initiator for polymerizing the monomers, a conventional one can be used at a conventional temperature range. Specific examples include benzoyl peroxide, lauryl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), orthochlorobenzoyl peroxide, orthomethoxy Mention may be made of benzoyl peroxide and others. As the polymerization method, a method under normal pressure or under high pressure may be arbitrarily adopted. The magnetic powder used to obtain the magnetic toner is a substance that is strongly magnetized in the direction of a magnetic field, preferably black in color, chemically stable, and with a particle size of 1 micron or less. A fine powder of is preferred, and magnetite (triiron tetroxide) is most preferred from these points of view. Typical magnetic or magnetizable substances include cobalt,
Metals such as iron, nickel; aluminum, cobalt, copper, iron, magnesium, nickel, tin,
Alloys and mixtures of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium; aluminum oxide, iron oxide,
Copper oxide, nickel oxide, zinc oxide, titanium oxide,
and metal compounds including metal oxides such as magnesium oxide; refractory titides such as vanadium titride and chromium titide; carbides such as tungsten carbide and silica carbide; ferrites and mixtures thereof can be used. These magnetic powders preferably have an average particle size of about 0.01 to 1 micron. The content in the toner is preferably about 50 to 300 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the polymer component. Particularly preferably, the amount is 90 to 150 parts by weight per 100 parts by weight of the polymer component. The inorganic dispersants used in the present invention, which are charged to the opposite polarity to the dispersed particles of the polymerization composition when dispersed in water, include anionic ones such as colloidal silica (SiO ₂ ) and bentonite (SiO ₂ / Al ₂ O ₃ ), and cationic ones include aluminum oxide (Al ₂ O ₃ ). The smaller the particle size of the inorganic dispersant, the more effective the effect can be exerted even with a small amount. For example, colloidal silica "Aerosil" (manufactured by Degussa) has an average primary particle size of 40 to 70 mμ, and has a pH of 4% by weight in water.
3.6 to 4.3. In addition, aluminum oxide "Aluminum Oxide C" (manufactured by Degussa) is extremely fine and highly pure with an average primary particle diameter of 20 mμ, exhibits an isoelectric point PH≒9, and has a high purity on the neutral or acidic side. use. These inorganic dispersants are used in an amount of 0.1% by weight or more, preferably 0.2% by weight based on the polymerizable monomer.
It is used in the above ratio. There is no need to set an upper limit, but even if 2% by weight or more is used, no further effect on polymerization stability or finer particle size is observed, but such use is prohibited. It's not even a thing. As described above, the present invention includes a polymerizable monomer, a crosslinking agent, a low molecular weight polyolefin having a softening point of 100 to 180°C made of polyethylene or polypropylene or an ethylene-propylene copolymer, an ionic substance, a coloring agent, etc. When a polymerization composition containing the above particles is dispersed and suspended in water, the interface of the dispersed particles is positively or negatively charged by the ionic substance. On the other hand, the inorganic dispersant is negatively or positively charged, contrary to the dispersed particles of the polymerization composition, and therefore the particles of the inorganic dispersant firmly adhere to the surface of the dispersed particles due to ionic bonds. , the surfaces of the dispersed particles are coated with the inorganic dispersant.
The dispersed particles in this state are extremely stable in water, and even when the tackiness of the dispersed particles increases during the initial and middle stages of polymerization of the polymerizable monomer, the dispersed particles do not coalesce. In this way, the inorganic dispersant is attached to the surface of the dispersed particles of the polymerization composition by ionic bonding, so that unlike conventional dispersants, the dispersant simply adsorbs to the surface of the dispersed particles, or the inorganic dispersant adheres to the surface of the dispersed particles of the polymerization composition. Unlike those that prevent the dispersion particles from coalescing by intervening in the dispersant, the adhesion force of the dispersant to the dispersed particles is much greater, and once attached, they will not separate.
Moreover, since it adheres to the entire surface of the dispersed particles, coalescence of the dispersed particles is completely prevented until the polymerization is completed. Furthermore, since the dispersed particles once formed do not coalesce as described above, by mechanically stirring the polymerization composition in water and dividing it into fine particles,
Polymer particles having the required toner particle size (1 to 50 microns) can be reliably obtained. Further, the polymerization composition may be divided and dispersed simultaneously with the polymerization, but there is no problem even before the start of the polymerization because the state is maintained. In order to obtain a toner with a preferable particle size,
The stirring may be performed to a shearing force of 10 ³ to ^{10 6} dynes/cm ² . Without being bound by any theory, the mechanism of the chemical stabilizing effect of the dispersed particles described above is as follows:
It can be explained as follows. (1) Since bentonite (SiO ₂ /Al ₂ O ₃ ) and colloidal silica (SiO ₂ ) contain a small amount of silanol groups, they dissociate into SiO ⁻ and H ⁺ in water. That is, bentonite and colloidal silica are anionic dispersants that are negatively charged in water. Therefore, the cationic polymerizable monomer etc. will strongly bond ionicly to the positively charged dispersed particles of the polymerization composition in the water, completely covering the surface of the dispersed particles. Since the inorganic dispersant adhering to the surface of the dispersed particles forms a hydration layer around the dispersed particles, the dispersed particles are significantly stabilized. Therefore, even when the tackiness of the dispersed particles increases during the initial and middle stages of polymerization of the monomer in the dispersed particles,
Coalescence of dispersed particles does not occur. (2) Aluminum oxide (Al ₂ O ₃ ) is a cationic dispersant that has an isoelectric point of PH≈9 and is positively charged on the neutral to acidic side. Therefore, it ionically bonds with the negatively charged dispersed particles of the polymerization composition to achieve the same effect as described above. It was confirmed by electrophoresis that the dispersed particles of the polymerization composition had a structure in which the inorganic dispersant was firmly bound to the surface thereof. That is, it was found that when an anionic inorganic dispersant was used, the sample migrated toward the anode, and the particle migration surface (particle surface when dried) was negatively charged. It was also found that the sample using a cationic inorganic dispersant migrated toward the cathode, and the particle migration surface was positively charged. In this way, the polymerizable monomer is polymerized while the dispersed particles of the polymerization composition generated by mechanical stirring are kept stable, and the resulting polymer particles are as follows: Each particle is spherical and has a uniform particle size distribution, and can be used as a toner for practical use as is. As described above, according to the present invention, a toner containing necessary components can be obtained in substantially one step without requiring complicated steps or including a pulverization step. The toner thus obtained contains a specific low-molecular-weight polyolefin dispersed in the form of fine particles in crosslinked polymer particles, and the low-molecular-weight polyolefin has properties as a lubricant or a mold release agent; Since the polymer is crosslinked and has high viscoelasticity and high cohesive force when melted, it has excellent non-offset properties. Moreover, the crosslinked polymer has a wide molecular weight distribution and has a low molecular weight portion, so that the fixing properties are not inhibited. Since the manufacturing process does not include a kneading process, the molecular chains of the polymer are not cut, and a toner made of a polymer in the desired crosslinked state can be reliably obtained, and the above effects can be fully obtained. can. In addition to the above-mentioned excellent non-offset property, a great anti-wrapping effect can be obtained, and the trouble of the transfer paper supporting the toner image being wrapped around the outer peripheral surface of the heating roller during fixing can be reliably prevented.
This is because the polymerizable monomer is polymerized in the presence of a specific low-molecular-weight polyolefin that is mixed, dispersed, or dissolved in the polymerizable monomer, and the toner particles are formed with the low-molecular-weight polyolefin uniformly dispersed in the form of fine particles. This is because the low molecular weight polyolefin is contained in the toner particles, and as a result, the low molecular weight polyolefin is not present on its own, so that its tackiness is suppressed, and moreover, great releasability is imparted to the toner particles. For this reason, the toner does not suffer from disadvantages such as carrier contamination, electrostatic image support contamination, and decreased fluidity, which generally occur when low molecular weight polyolefins are contained. In addition, since the colorant is contained in the polymerization composition, the dispersibility of the colorant in the polymer particles is improved, and high image density can be obtained, and the toner has stable triboelectric charging properties. Therefore, the charging property is stable even when copying is performed many times, and excellent durability can be obtained. On the other hand, when the melt-kneading method is used, the colorant is poorly dispersed, so when copying is performed many times, the colorant becomes liberated from the polymer particles, contaminating the carrier and photoreceptor. The disadvantage is that the image density decreases quickly. Further, since the toner according to the present invention is a crosslinked polymer, it has high impact resistance and is not crushed by stirring during development.
Therefore, fine powder produced by crushing does not adhere to the surface of the carrier and deteriorate its characteristics, or it does not adhere to the electrostatic image support. Furthermore, for the same reason, the toner has excellent moisture resistance and durability, has a high shelf life and does not cause blocking, and has high fluidity because each particle is spherical. . Note that when the toner according to the present invention is mixed with a carrier and used as a component of a so-called two-component developer, the carrier does not require any special properties, and if it contains a magnetic material, it can be used as is. It can be used as a one-component toner. Examples of the present invention will be described below, but the present invention is of course not limited to these. Note that "parts" represent parts by weight. Example 1 300 parts of styrene and low molecular weight polypropylene "Viscol 550P" (manufactured by Sanyo Chemical Industries, Ltd., softening point
Triethylene glycol methacrylate (15 parts) was added and heated to 150°C while stirring.
2.0 parts triiron tetroxide powder "Mapico Black BL-500"
(manufactured by Titan Kogyo Co., Ltd.) 200 parts methylene blue chloride (charge control agent) 1 part diethylaminoethyl acrylate 1.5 parts benzoyl peroxide 1 part The above substances were mixed to prepare a polymerization composition.
On the other hand, take 1.5 parts of colloidal silica "Aerosil 200" (manufactured by Degussa) into a separable flask with a capacity of 2, add distilled water, add the above polymerization composition, and rotate at 1000 r.p.m. using a microagitor (manufactured by Shimazaki Seisakusho). Raise the temperature to 90℃ while stirring at pm,
It was kept at this temperature. The particle size range of the dispersed particles after 15 minutes had passed since the temperature was raised to 90°C was 15 to 20 microns. Although the polymerization reaction proceeded in this manner for 6 hours, no change in particle size was observed until the polymerization was completed. After the polymerization was completed, the solid particles were filtered and dried to obtain a one-component toner with an average particle size of 17 microns. This will be referred to as "Sample 1". Example 2 “Mapiko Black BL-” was used as triiron tetroxide powder.
100'' (manufactured by Titan Kogyo Co., Ltd.) 200 parts, 300 parts of methyl methacrylate as a polymerizable monomer, and tetramethylolmethanetetraacrylate as a crosslinking agent.
0.5 parts, 5 parts of polypropylene "Viscol 550P" as a low molecular weight polyolefin, 2 parts of N-n-butoxyacrylamide as an ionic substance, and 2 parts of colloidal silica "Aerosil 380" (manufactured by Degussa) as an inorganic dispersant. A one-component toner having an average particle size of 17 microns was obtained in exactly the same manner as in Example 1, except for using the following ingredients. This will be referred to as "Sample 2." Example 3 “Mapiko Black BL-” was used as triiron tetroxide powder.
100” 100 copies and “Mapiko Black BL-500” 100 copies
part, 220 parts of styrene as a polymerizable monomer and n-
80 parts of butyl methacrylate, polypropylene "Viscol 550P" as low molecular weight polyolefin
10 parts, 4 parts of diethylaminoethyl methacrylate as an ionic substance, 2 parts of ethylene glycol methacrylate as a crosslinking agent, and colloidal silica "Aerosil 200" as an inorganic dispersant.
A one-component toner having an average particle size of 17 microns was obtained in exactly the same manner as in Example 1, except that 4 parts were used. This will be referred to as "Sample 3." Example 4 250 parts of methyl methacrylate was mixed with 10 parts of low molecular weight polypropylene "Viscoll 550P" and heated to a temperature of 150°C while stirring. Trimethylolpropane trimethacrylate.
2.0 parts triiron tetroxide powder "Mapico Black BL-100"
150 parts triiron tetroxide powder "Toda Color EPT-1000" (manufactured by Toda Kogyo Co., Ltd.) 100 parts Nigrosine base "EX" (manufactured by Orient Chemical Co., Ltd. charge control agent) 0.5 parts dicocoamine 3 parts azobisisobutyronitrile 1 part or more A composition for polymerization was prepared by mixing the following substances.
On the other hand, take 3 parts of colloidal silica "Aerosil Mox 170" (manufactured by Degussa) in a separable flask with a capacity of 2, add distilled water, add the above composition for polymerization, and mix it with a TK homomixer (Tokushu Kika Kogyo Co., Ltd.). The temperature was increased while stirring at a rotation speed of 3000 r.pm.
The temperature was raised to 80°C and maintained at this temperature. The particle size range of the dispersed particles after 30 minutes of heating was 10 to 15 microns. After that, the number of revolutions is increased using a regular stirrer.
The polymerization reaction was continued for 6 hours while stirring at 100 rpm to complete the polymerization, but no change in particle size was observed. After the polymerization was completed, the solid particles were filtered and dried to obtain a one-component toner with an average particle size of 13 microns. This will be referred to as "Sample 4." Example 5 “Toda Color EPT” was used as triiron tetroxide powder.
1000'' 250 parts, 160 parts of methyl methacrylate and 90 parts of n-butyl methacrylate as polymerizable monomers, 3 parts of diethylene glycol methacrylate as a crosslinking agent, 40 parts of polypropylene ``Viscol 550P'' as a low molecular weight polyolefin, and an ionic substance. Example 4 except that 1.5 parts of dodecylamine was used as an inorganic dispersant and 1.5 parts of colloidal silica "Aerosil 200" was used as an inorganic dispersant.
A one-component toner having an average particle size of 13 microns was obtained in exactly the same manner as described above. This will be referred to as "Sample 5." Example 6 “Mapiko Black BL” was used as triiron tetroxide powder.
-500” 100 copies and “Toda Color EPT-1000” 150 copies
240 parts of styrene and 10 parts of methyl acrylate as polymerizable monomers, 30 parts of trimethylolpropane triacrylate as a crosslinking agent, and polypropylene "viscol" as a low molecular weight polyolefin.
550P" and 5 parts of dimethylaminoethyl methacrylate as an ionic substance, and colloidal silica "Aerosil" as an inorganic dispersant.
A one-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 4, except that 5 parts of "Mox170" were used. This will be referred to as "Sample 6". Example 7 400 parts of styrene and 50 parts of methyl methacrylate
and 50 parts of n-butyl methacrylate.
Diethylene glycol methacrylate 25 parts "Carbon Black MA-600" (manufactured by Mitsubishi Chemical Industries, Ltd.) 15 parts "Azo Oil Black (R)" (national aniline) Charge Control Agent (manufactured by KK) 1 part dodecylamine 2 parts lauroyl peroxide 2 parts The above substances were mixed to prepare a polymerization composition.
On the other hand, take 2 parts of colloidal silica "Aerosil 380" in a separable flask with a capacity of 2, add distilled water, add the above polymerization composition, and bring the temperature to 70°C while stirring at a rotation speed of 1000 rpm using a micro agitator. The temperature was increased and maintained at this temperature. The particle size range of the dispersed particles after 15 minutes of heating was 15 to 20 microns. Although the polymerization reaction proceeded in this manner for 6 hours, no change in particle size was observed until the polymerization was completed. After the polymerization was completed, the solid particles were filtered and dried to obtain a two-component toner with an average particle size of 17 microns. This will be referred to as "Sample 7." Example 8 40 parts of "Raven 1250" (manufactured by Columbian) as carbon black, 400 parts of styrene as polymerizable monomers, 50 parts of methyl methacrylate and 10 parts of acrylonitrile, 2 parts of triethylene glycol methacrylate as a crosslinking agent, Polypropylene “Viscol 550P” as molecular weight polyolefin
40 parts, and 3 parts of methacrylic acid as the ionic substance, and 3 parts of aluminum oxide "Aluminum Oxide C" (manufactured by Degussa) as the inorganic dispersant. A two-component toner with a diameter of 17 microns was obtained. This will be referred to as "Sample 8." Example 9 “Monarch 1100” as carbon black
(manufactured by Cabot) 20 parts, 450 parts of styrene as polymerizable monomers, 40 parts of n-butyl methacrylate and 10 parts of n-butyl acrylate, 20 parts of tetramethylolmethanetetraacrylate as a crosslinking agent
Example 7 except that 25 parts of polypropylene "Viscol 550P" was used as the low molecular weight polyolefin, 5 parts of diethylaminoethyl methacrylate was used as the ionic substance, and 5 parts of colloidal silica "Aerosil 200" was used as the inorganic dispersant. A two-component toner having an average particle size of 17 microns was obtained in exactly the same manner as described above. This will be referred to as "Sample 9." Example 10 450 parts of styrene and 50 parts of n-butyl acrylate
25 parts of low molecular weight polypropylene "Viscol 550P" was added to the mixture with 1 part of trimethylolpropane triacrylate and heated to 150°C while stirring.
2.5 parts "Carbon Black #2300" (manufactured by Mitsubishi Chemical Industries, Ltd.) 25 parts "Oil Black BW" (manufactured by Orient Chemical Co., Ltd., charge control agent) 0.5 parts Diethylaminoethyl methacrylate 4 parts 2,2'-Azobis-(2,4 -dimethylvaleronitrile) 2 parts A composition for polymerization was prepared by mixing the above substances.
On the other hand, take 4 parts of colloidal silica "Aerosil 200" in a separable flask with a capacity of 2, add distilled water, add the above composition for polymerization, and mix with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 3000 r.
The temperature was raised to 65°C while stirring at pm and maintained at this temperature. The particle size range of the dispersed particles after 30 minutes of heating was 10 to 15 microns. Thereafter, the polymerization reaction was allowed to proceed for 6 hours while stirring at a rotational speed of 100 rpm using an ordinary stirrer, and the polymerization was completed.
No change in particle size was observed. After the polymerization was completed, the solid particles were filtered and dried to obtain a two-component toner with an average particle size of 13 microns. This will be referred to as "Sample 10." Example 11 30 parts of "Regal 500R" (manufactured by Kabot Corporation) as carbon black, styrene as polymerizable monomer
425 parts and 75 parts of n-butyl methacrylate, 20 parts of trimethylolpropane triacrylate as a crosslinking agent, 50 parts of polypropylene "Viscol 550P" as a low molecular weight polyolefin, and 3 parts of dodecylamine as an ionic substance, and an inorganic dispersant. Colloidal silica as “Aerosil
A two-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 10, except that 3 parts of "Mox170" were used. This will be referred to as "Sample 11." Example 12 25 parts of "Raven 850" (manufactured by Columbian) as carbon black, 430 parts of styrene as polymerizable monomers, 20 parts of methyl methacrylate, and n-
50 parts of butyl acrylate, 50 parts of diethylene glycol methacrylate as a crosslinking agent, polypropylene "Viscoll" as a low molecular weight polyolefin.
550P" and 6 parts of diethylaminoethyl methacrylate as an ionic substance, and colloidal silica "Aerosil" as an inorganic dispersant.
A two-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 10, except that 6 parts of ``200'' was used. This will be referred to as "Sample 12." Example 13 In the formulation of the polymerization composition in Example 10, an average particle size A two-component toner with a diameter of 13 microns was obtained. This will be referred to as "Sample 13." Comparative Example 1 A one-component toner with an average particle size of 17 microns was obtained in the same manner as in Example 1, except that the crosslinking agents triethylene glycol methacrylate and polypropylene were excluded from the formulation of the polymerization composition in Example 1. . This will be referred to as "comparative sample 1." Comparative Example 2 A one-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 4, except that the crosslinking agent trimethylolpropane trimethacrylate was excluded from the formulation of the polymerization composition in Example 4. This will be referred to as "comparative sample 2." Comparative Example 3 A two-component toner having an average particle size of 17 microns was obtained in exactly the same manner as in Example 7, except that the crosslinking agents diethylene glycol methacrylate and polypropylene were excluded from the formulation of the polymerization composition in Example 7. This will be referred to as "comparative sample 3." Comparative Example 4 A two-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 10, except that the crosslinking agent trimethylolpropane triacrylate was excluded from the formulation of the polymerization composition in Example 10. This will be referred to as "comparative sample 4." Comparative Example 5 A one-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 4, except that polypropylene was excluded from the formulation of the polymerization composition in Example 4. This will be referred to as "comparative sample 5." Comparative Example 6 A two-component toner having an average particle size of 13 microns was obtained in exactly the same manner as in Example 10, except that polypropylene was excluded from the formulation of the polymerization composition in Example 10. This will be referred to as "comparative sample 6." Comparative Example 7 Crosslinked polymer particles with an average particle size of 17 microns were obtained in the same manner as in Example 7, except that carbon black, charge control agent, and polypropylene were excluded from the formulation of the polymerization composition in Example 7. . 100 parts of this crosslinked polymer particles and "Carbon Black MA
-600'', 0.2 parts of charge control agent ``Azo Oil Black (R)'', and 6 parts of low molecular weight polypropylene ``Viscol 550P'' were mixed and melted and kneaded.
The resulting agglomerate was pulverized and the powder was classified to produce a two-component toner having an average particle size of 17 microns. This will be referred to as "comparative sample 7." The results of tests conducted on the above samples and comparative samples are shown below. Samples 1 to 6 and Comparative Samples 1, 2, and 5 were subjected to an offset test and a wrap test. First, in the offset test, each sample was tested on the electronic copying machine "U-Bix T".
(manufactured by Konishiroku Photo Industry Co., Ltd.), the electrostatic charge image formed was developed, and the resulting toner image was 64 g/
m ² transfer paper, the surface layer of which is made of Teflon (tetrafluoroethylene manufactured by Dupont) and the surface layer of which is silicone rubber "KE".
-1300RTV" (manufactured by Shin-Etsu Chemical Co., Ltd.) and a fixing device consisting of a pressure roller, the transferred image was fixed at a linear speed of 150 mm/sec, and then the transfer paper without the toner image was similarly processed under the same conditions. The temperature at which the offset phenomenon occurs was determined by variously setting the temperature of the heating roller to examine the presence or absence of stains on the transfer paper due to the offset phenomenon. As a result, in the case of Samples 1 to 6, no offset phenomenon was observed even when the temperature of the heating roller was raised to 240°C, whereas in the case of Comparative Samples, as shown in Table 1. An offset phenomenon was observed depending on the temperature. In the winding test, the same equipment and transfer paper as in the offset test were used under the same conditions, and a solid black toner image with a width of 3 cm was formed on the leading edge of the transfer paper and this was fixed. The temperature of the heating roller of the fixing device was set variously, and the lowest temperature at which the transfer paper did not wrap was determined. As a result, in the case of samples 1 to 6, the temperature
At temperatures above 170°C, no coiling occurred at all, whereas in the case of the comparative sample, the first
Coiling occurred at temperatures below the values shown in the table.

[Table] From the results of these tests, it was found that Samples 1 to 6, which are toners made of crosslinked polymers containing a specific low molecular weight polyolefin according to the present invention, have extremely excellent non-offset properties and non-wrapping properties; Comparative Sample 1, a toner made of a non-crosslinked polymer that does not contain a low molecular weight polyolefin, has low non-offset and non-wrapping properties, and a toner that contains a low molecular weight polyolefin but is not crosslinked. Comparative Sample 2 has the same non-wrapping properties as the one according to the present invention, but the non-offset properties are still lower, and a toner made of a crosslinked polymer that does not contain a low molecular weight polyolefin.
Although Comparative Sample 5 has some degree of non-offset property, it is clear that the non-winding property is small. Samples 7 to 13 and comparative samples 3, 4, 6 and 7
An offset test, a winding test, and a fluidity test were conducted on the material. In the offset test, each sample
is mixed with 95 parts of iron powder carrier to make a developer.
The offset test was conducted in the same manner as in the offset test, except that "U-Bix V" (manufactured by Konishiroku Photo Industry Co., Ltd.) was used as the electronic copying machine. As a result, in the case of Samples 7 to 13, no offset phenomenon was observed even when the temperature of the heating roller was raised to 240°C, whereas in the case of the comparative samples, as shown in Table 2. An offset phenomenon was observed depending on the temperature. The winding test was conducted in the same manner as in the winding test, except that the same developer and electronic copying machine as in the offset test were used. As a result, in the case of Samples 7 to 13, no wrapping occurred at all when the temperature of the heating roller was 170°C or higher, whereas in the case of the comparative sample, no wrapping occurred at temperatures below the temperature shown in Table 2. Winding occurred.

[Table] From the above test results, toners according to the present invention, Samples 7 to 13, are excellent in both non-offset and non-wrapping properties, but toners that do not contain low molecular weight polyolefin or are not crosslinked polymers ,
Comparative samples 3, 4, and 6 have the same weaknesses as comparative samples 1, 2, and 5, respectively, and are crosslinked polymers containing low molecular weight polyolefins, which were mixed in by melt kneading. It is clear that the toner Comparative Sample 7 is inferior to the toner according to the present invention in both non-offset and non-wrapping properties. Furthermore, in the fluidity test, each sample
50g was sampled and the time required for it to fall down a predetermined distance was determined using a powder tester (manufactured by Hosokawa Iron Works). The results are shown in Table 3. From the results of this test, comparative sample 7
It is clear that the toner particles are obtained by a pulverization process and the particles are not spherical, and furthermore, the low molecular weight polyolefin is not uniformly dispersed in the toner particles, so the fluidity is extremely low.

[Table] Copying tests were conducted on samples 1 to 13. As a result of this test, excellent copy images with high image density and clarity were obtained for all samples, and even when the number of copies reached 40,000, the image density was still high and the heating roller of the fuser No toner stain was observed on the photoreceptor, and no toner stain was observed on the photoreceptor, and a copy image as good as that at the initial stage of copying was obtained. On the other hand, since Comparative Sample 7 is a toner manufactured by melt-kneading and pulverization, the colorant and low molecular weight polyolefin are not uniformly dispersed in the toner, and as a result, the number of copies is 5000.
After reaching the 5th cycle, fogging and a decrease in image density are observed in the copied image, the copied image becomes unclear, and furthermore, due to poor offset properties, toner contamination of the heating roller occurs, and the wrapping resistance deteriorates. Due to the defect, paper jams occurred in the heat roller of the transfer paper, and furthermore, the toner contamination of the photoreceptor became significant due to the free colorant and low molecular weight polyolefin.

Claims (1)

[Scope of Claims] 1. A polymerizable monomer, a crosslinking agent for the polymerizable monomer, and a polyethylene or polypropylene or ethylene-propylene copolymer having a softening point.
A polymerization composition comprising a low molecular weight polyolefin having a temperature of 100 to 180°C, an ionic substance, and a colorant, the dispersed particles of which are charged to one polarity when dispersed in water; 1. A method for producing a toner for developing an electrostatic image for heat roller fixation, comprising polymerizing and crosslinking the polymerizable monomer in a state in which an inorganic dispersant charged to the other polarity is dispersed and suspended in water. 2. The heat roller fixing device according to claim 1, wherein the polymerization composition contains one selected from cationic polymerizable monomers, poorly water-soluble amines, and anionic polymerizable monomers. A method for producing a toner for developing electrostatic images. 3. The toner for developing electrostatic images for heat roller fixation according to claim 1 or 2, wherein the ratio of the crosslinking agent to the polymerizable monomer in the polymerization composition is 0.005 to 20% by weight. manufacturing method. 4. Claims 1 and 2, wherein the low molecular weight polyolefin in the polymerization composition is dissolved or uniformly dispersed in the polymerizable monomer.
3. A method for producing a toner for developing an electrostatic image for thermal roller fixation according to item 1 or 3. 5 The ratio of the low molecular weight polyolefin to the polymerizable monomer in the polymerization composition is 1
The method for producing an electrostatic image developing toner for thermal roller fixation according to any one of claims 1 to 4, wherein the toner is 20% by weight. 6 The dispersed particles of the polymerization composition have a particle size of 1 to 50
The method for producing a toner for developing an electrostatic image for fixing with a hot roller according to any one of claims 1 to 5, wherein the toner is dispersed and suspended as micron particles. 7 The dispersion and suspension of the polymerization composition has a shear force of 10 ³
7. The method for producing an electrostatic image developing toner for heat roller fixing according to claim 6, which is carried out by stirring at a rate of 10 ⁶ dynes/cm ² . 8. The method for producing an electrostatic image developing toner for heat roller fixation according to claim 7, wherein the stirring is performed up to the initial stage of polymerization of the polymerizable monomer.