JP3213783B2 - toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner applied to a one-component developing system or a two-component developing system.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
JP-A (U.S. Pat. No. 3,666,363) and JP-B-43-24748 (U.S. Pat.
Many methods are known, for example, a photoconductive substance is used, an electric latent image is formed on a photoreceptor by various means, and the latent image is then developed. (Hereinafter referred to as "toner"), and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, pressure and heat fixing rollers or solvent vapor to obtain a copy. Things.

In the case where a step of transferring a toner image is provided, a step for removing residual toner on the photoconductor is usually provided.

As a developing method for visualizing an electric latent image using toner, for example, US Pat. No. 2,874,06
No. 3,618,552, and the cascade developing method described in U.S. Pat. No. 2,618,552, and U.S. Pat. No. 2,221,776. Powder cloud method, US Patent 3,909,2
A method using a conductive magnetic toner described in Japanese Patent No. 58-58 is known.

As a toner applied to these developing methods, a fine powder in which a dye or a pigment is dispersed in a natural or synthetic resin is conventionally used. For example, a colorant dispersed in a binder resin such as polystyrene is 1 to 30 μm.
Particles pulverized to about m are used as toner. Further, as the magnetic toner, one containing magnetic particles such as magnetite is used, and in the case of a system using a so-called two-component developer, the toner is usually combined with carrier particles such as glass beads and iron powder. Used as a mixture.

As the positive charge controlling agent used in such a toner for dry development, for example, a quaternary ammonium compound and an organic dye, in particular, a basic dye and a salt thereof are generally used, and a nigrosine base and a nigrosine are often used. Used as a charge control agent. These are usually added to a thermoplastic resin, melt-dispersed by heating, finely pulverized, and adjusted to an appropriate particle size as needed, before use.

However, these charge control agents are liable to cause a phenomenon in which charge controllability is reduced due to mechanical shock, friction, changes in temperature and humidity conditions, and the like.

Therefore, when a toner containing these as a charge control agent is developed using a copying machine, the toner may be deteriorated during the durability as the number of copies increases.

Further, since it is extremely difficult to uniformly disperse these charge control agents in a thermoplastic resin, there is a problem that a difference occurs in a triboelectric charge amount between toner particles obtained by pulverization. Have.

[0010] For this reason, various methods for more uniformly dispersing have been conventionally performed. For example, when using a basic nigrosine dye, in order to improve the compatibility with the thermoplastic resin, it is used in the form of a salt with a higher fatty acid, but often the unreacted fatty acid or the dispersed component of the salt, The toner is exposed on the surface of the toner and contaminates the carrier or the toner carrier, causing a decrease in the fluidity of the toner, fog, and a decrease in image density.

Alternatively, in order to improve the dispersibility of the charge control agent in the resin, a method of mechanically pulverizing and mixing the charge control agent powder and the resin powder in advance, followed by hot-melt kneading has been proposed. However, the actual dispersion failure cannot be avoided, and the uniformity of charge sufficient for practical use has not yet been obtained.

Further, a positively chargeable monomer such as dimethylaminoethyl methacrylate is copolymerized or graft-polymerized into the binder resin, thereby introducing an amino group to make the binder resin itself positively chargeable. Attempts have been made to provide a uniform charge to the toner.

However, the positive chargeability of the binder resin as described above is not constant, and the magnitude of frictional force between toner particles, between toner and carrier, or between toner and toner carrier such as sleeve, and It varies greatly depending on the friction probability, and it may be difficult to always give a constant and stable positive charge to the toner. Therefore, the positive chargeability of the toner when the appropriate friction is not obtained is very unstable, and the copy image obtained by the toner becomes an image with much fog and scattering.

On the other hand, when excessive friction is applied, the amount of positively charged electric charges on the toner surface becomes extremely large, so that only an image having a large amount of roughness and a low density can be obtained.

As a method for obtaining a developer having a positive charge control property, there is a method disclosed in Japanese Patent Publication No. 53-22447.
This is a method in which a metal oxide powder treated with aminosilane is contained as a component of the developer. But,
When this method was studied in detail, for example, colloidal silica, alumina, titanium dioxide, zinc oxide, iron oxide,
When a variety of aminosilane compounds are treated with γ-ferrite and magnesium oxide to obtain a developer according to the examples described in the specification, a developer exhibiting practically sufficient characteristics in any combination Was not obtained, and it became clear that there were some problems.

That is, many developers cannot maintain the characteristics desirable for faithfully reproducing a latent image for a long period of time. At first, those exhibiting desirable performance cannot maintain the initial characteristics after long-term continuous use, and thus cannot be used. That is, fogging occurs, toner is scattered around edges in copying a line drawing, and image density is also reduced.

Another problem is that when development and transfer are performed under high-temperature and high-humidity environmental conditions, a decrease in image density, scattering of line images, white spots, fog, and the like occur.

Another method for obtaining a positively chargeable developer is described in JP-A-59-201063. This is a method in which a fine silica powder treated with a silicon oil containing an amine in a side chain is contained as a component of the developer, instead of the fine metal powder treated with the aminosilane described above.

According to this method, the problem of the developer containing the fine metal powder treated with aminosilane can be compensated, and a developer having substantially sufficient characteristics can be obtained.

[0020]

However, as copiers and printers using the electrophotographic process have become more and more widespread year by year, the use cases in more severe environments have increased. In particular, in a low humidity environment, the toner is excessively charged, and various problems occur.

In the one-component developing method using a magnetic toner or the like, for example, a phenomenon occurs in which the coat layer of the toner on the developing sleeve becomes uneven.

On the other hand, in the two-component developing system, phenomena such as image density bleeding and fogging occur.

Accordingly, an object of the present invention is to provide a toner coating layer on a developing sleeve in a one-component developing system which is not charged excessively even in a low-humidity environment. An object of the present invention is to provide a positively chargeable toner that does not generate fog or the like.

[0024]

The above objects can be attained by the following inventions.

That is, the present invention relates to a toner containing a binder resin and a triphenylmethane compound, wherein the binder resin is a styrene copolymer and has a group containing a nitrogen atom in a side chain. A toner characterized in that the toner contains fine particles that have been subjected to a heat treatment at a heating temperature of 180 to 320 ° C. in the presence of oxygen after being treated with a polymer or oligomer.

The heat-treated fine particles according to the present invention are preferably present on the toner surface.
It is particularly preferable that the fine particles in which the nitrogen-containing compound adheres, adsorbs, and reacts on the surface are externally added to the toner.

Examples of the compound containing a nitrogen atom include compounds having a nitrogen-containing atom group such as an amino group, an amide group and a nitro group in a side chain or a main chain. Among them, compounds having an amino group are exemplified. preferable.

As the amino group, primary amine, 2
Any of a tertiary amine, a tertiary amine and a quaternary amine may be used. For example, the following are mentioned.

[0029] _{-NH 2 -NH-CH 3, -NH} -C 2 H 5, -NH-C 3 H 7 -N (CH 3) 2, -N (C 2 H 5) 2, -NH-C 2 _{H 4 -NH 2 -N (C 3} H 6) 2, -NH-C 2 H 4 -N (CH 3) 2 -N (C 4 H 9) 2 -N (CH 3) + 3 · Cl -, ^{_{-N (CH 3) + 3 ·}} HCO
^{_{- 3 -N (C 2 H 5}} ) + 3 · Cl -, -N (C 2 H 5) + 3 · HC
^{_{O - 3 -N (C 3 H}} 7) + 3 · Cl - -N (C 4 H 9) + 3 · Cl -

[0030]

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As the compound containing a nitrogen atom, a polymer or oligomer having a group containing a nitrogen atom in a side chain is used.

[0032]

[0033]

[0034]

[0035]

The polymer / oligomer having a nitrogen atom in the side chain is not particularly limited, but among them, silicone-based polymers / oligomers such as silicone varnish and silicone oil are preferred.

As the silicone-based polymer / oligomer having a nitrogen atom in the side chain, those having a structure represented by the following formula can be generally used.

[0038]

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(Where R ₁ and R ₃ represent hydrogen, an alkyl group, an aryl group or an alkoxy group, and R ₂ represents
R ₄ and R ₄ represent an alkylene group or a phenylene group;
₅ represents hydrogen, an alkyl group or an aryl group. Also, R ₂ need not be present. However, the above-mentioned alkyl group, aryl group, alkylene group and phenylene group may contain an amine, and may have a substituent such as halogen as long as the chargeability is not impaired. R ₆ is a substituent containing a nitrogen atom. N is a number of 1 or more, and m is a positive number including 0. )

The nitrogen equivalent of the silicone polymer / oligomer used in the present invention is preferably 10,000 or less, more preferably 300 to 2,000. Here, the nitrogen atom equivalent is a value obtained by dividing the molecular weight by the number of nitrogen atoms per molecule by the equivalent per nitrogen atom (g / eqio). These may be used alone or in a mixture of two or more.

Silicone polymer / oligomer 2
The viscosity at 5 ° C. is 10 to 1,000 cSt,
Preferably 10 to 500 cSt, more preferably 10 to 500 cSt
Those of 200 cSt are preferred.

Examples of the fine particles for allowing the compound containing a nitrogen atom subjected to heat treatment in the presence of oxygen to be present on the surface include the following inorganic fine particles and resin particles.

As the inorganic fine particles, Na, Mg, Al,
Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe,
Co, Ni, Cu, Zn, Ga, Ge, Sr, Y, Z
r, Nb, Mo, Tc, Ru, Rh, Pd, Ag, C
Examples thereof include metals such as d, In, Sn, Ba, Ce and Pb, particles of oxides, sulfides, double oxides and salts of these metals, and carbon black.

Among these, Al, Si and Ti
Is preferred.

As the organic fine particles, styrene resin, acrylic resin, polyester resin, butanediene resin,
Examples include fine particles of a resin such as a polyurethane resin, a polyamide resin, an epoxy resin, a silicone resin, polyethylene, polypropylene, and polyvinylidene fluoride, and fine particles of a fatty acid, a fatty acid metal salt, and a fatty acid ester.

The specific surface area of these particles is 0.1
~ 500 m ² / g is preferred, more preferably 0.5 ~
450 m ² / g, and more preferably has a 1~400m ² / g.

The amount of the nitrogen atom-containing compound to be treated with respect to the fine particles is 0.1 parts by weight with respect to 100 parts by weight of the fine particles.
It is preferably from 70 to 70 parts by weight.

The effect of the fine particles treated with the compound having a substituent and an amino group is 0.01 to 20% by weight with respect to the toner, and particularly preferably 0.02% by weight. To 10% by weight, more preferably 0.0%
It is effective when 3 to 5% by weight is added.

The heat treatment is carried out by heating fine particles having a compound containing a nitrogen atom adhering, adsorbing or reacting on the surface thereof in the presence of oxygen.

The heating can be performed in an electric furnace or a fluidized bed, but when the compound containing a nitrogen atom is present on the surface of the fine particles, the heating is preferably performed in the fluidized bed. It is preferable in that it prevents

The heating temperature is preferably from 180 to 320 ° C, more preferably from 200 to 300 ° C. If the temperature is lower than 180 ° C., the effect of preventing excessive charging in a low-temperature environment cannot be obtained. 3
When the temperature exceeds 20 ° C., the decomposition of amino groups becomes remarkable, which is not preferable from the viewpoint of charge control. The heat treatment time varies depending on the heating time, but is preferably in the range of 10 minutes to 150 minutes.

By the heat treatment in the presence of oxygen, the compound containing a nitrogen atom changes to a state in which it can easily retain moisture even in a low humidity environment, and the moisture acts to release an excessively charged charge from the toner surface. . For this reason, the toner is not excessively charged even in a low humidity environment,
It is considered that non-uniformity of the toner coat layer on the developing sleeve in the one-component developing system and image density fog and fog in the two-component developing system will not occur.

The positively-chargeable toner of the present invention is used as a developing sleeve to be coated with a toner,
The effect is particularly obtained in the case where irregularities are formed by a plurality of spherical trace depressions.

As a method for obtaining the surface state, a blasting method using fixed particles can be used. As the fixed particles used at this time, for example, various rigid spheres made of a metal such as stainless steel, aluminum, steel, nickel and brass having a specific particle size, or various rigid classes such as ceramic, plastic and glass beads are used. You can do it.

The developing sleeve used in the present invention can also be obtained by performing blasting with regular particles on the surface on which random irregularities have been formed by blasting with irregular particles of various rigid bodies as described above. Can be obtained.

Further, a blast treatment method in which irregular particles and regular particles are simultaneously used is also possible. Arbitrary abrasive grains can be used as the irregular shaped particles.

A plurality of spherical dents having substantially the same diameter R can be formed by subjecting the sleeve surface to blasting using fixed particles having a specific particle size.

In the present invention, the diameter R of the plurality of spherical trace depressions formed on the surface of the sleeve is preferably 20 to 250 μm, and if the diameter R is less than 20 μm, contamination by components in the magnetic toner increases. . Conversely, if the diameter R exceeds 250 μm, the uniformity of the toner coat on the sleeve is undesirably reduced.

The shaped particles have a substantially curved surface and a diameter / minor axis ratio of 1 to 2 (preferably 1 to 2).
1.5, more preferably 1-1.2) spherical or spheroidal particles are preferred. Therefore, the shaped particles used for blasting the sleeve surface have a diameter (or long diameter) of 2
It is preferably from 0 to 250 μm.

For the pitch P and the surface roughness d of the surface of the sleeve subjected to the blasting treatment with the fixed particles, the surface of the sleeve is measured using a fine surface roughness meter (a sales agency: Taylor Hopson, Kosaka Laboratory, etc.). And the surface roughness d is
10-point average roughness (RZ) according to "JIS B 0601".

The interval between two straight lines, a straight line parallel to the average line of the portion extracted by the reference length L from the sectional curve, a straight line passing through the third highest peak from the highest, and a straight line passing through the third bottom of the deep valley Is expressed in micrometers (μm). Here, the reference length is L = 0.25 mm.

The pitch P is set at 0.
Those having a height of 1 μm or more are counted as one peak, and are obtained as follows by the number of peaks within the reference length of 0.25 mm.

[250 (μm)] / [Number of mountains included in 250 (μm) (μm)]

In the present invention, the pitch P of the irregularities on the surface of the sleeve subjected to the blast treatment with the fixed particles is 2 μm.
When P is less than 2 μm, sleeve contamination by components in the magnetic toner increases, which is not preferable.

The surface roughness d of the irregularities on the sleeve surface
Is preferably 5 μm or less, and when d exceeds 5 μm, an alternating voltage is applied between the sleeve and the latent image holding member to cause the magnetic toner to fly from the sleeve side to the latent image surface to perform development. This is not preferable because the electric field tends to concentrate on the uneven portion and cause the image to be disturbed.

Examples of the binder resin used in the toner of the present invention include styrene such as polystyrene, poly-P-chlorostyrene, and polyvinyltoluene, and monomers substituted with styrene; styrene-P-chlorostyrene copolymer, styrene-propylene. Copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer,
Styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-acryl-aminoacrylic copolymer,
Styrene-aminoacrylic copolymer, styrene-aminomethacrylic copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinylethyl Ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butanediene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic ester Styrene copolymers such as copolymers; polymethyl methacrylate;
Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, terpene resin,
Phenol resins, aliphatic or cycloaliphatic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used alone or in combination of two or more as needed.

In particular, when the binder resins particularly suitable for pressure fixing are limited to the following, the following resins can be used alone or in combination.

For example, polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide,
Poly-4-fluoroethylene, etc., epoxy resin, polyester resin, styrene-butanediene copolymer (monomer ratio 5-30: 95-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acryl) Acid ester copolymer, ethylene-methacrylic acid copolymer,
Ethylene-methacrylic acid ester copolymer, ethylene-
Vinyl chloride copolymer, ethylene-vinyl acetate copolymer,
Ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin and phenol-modified terpene resin.

When the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder.

As the carrier that can be used in the present invention, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads and the like, and the surfaces thereof are made of resin. And the like. The mixing ratio of toner and carrier is usually
(0.1-60): (99.9-40).

The toner of the present invention can be used as a magnetic toner by further containing a magnetic material. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, maghematite, and ferrite; iron, cobalt,
Metals such as nickel or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium And mixtures thereof.

These ferromagnetic materials have an average particle size of 0.1 to
It is preferably about 2 μm, more preferably about 0.1 to 1 μm, and the amount contained in the toner is about 20 to 200 parts by weight, particularly preferably 100 parts by weight, per 100 parts by weight of the resin component. 40 to 150 parts by weight per part.

As long as it does not adversely affect the toner of the present invention, it can be used in combination with a conventionally known charge control agent.

As the charge control agent, a triphenylmethane compound is used.

It is also preferable to include the following waxes in the toner from the viewpoint of improving the releasability from the fixing member at the time of fixing and improving the fixing property.

Paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, etc. Includes block copolymers and graft-modified products with vinyl monomers.

In addition, alcohols, fatty acids, acid amides,
Esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam and the like can also be used.

Among the waxes preferably used are low-molecular-weight polyolefins obtained by radical polymerization of olefins under high pressure or polymerization using a Ziegler catalyst, and low-molecular-weight polyolefins obtained by thermally decomposing by-products and high-molecular-weight polyolefins. A wax obtained from a hydrocarbon distillation residue obtained by using a catalyst from a synthesis gas consisting of polyolefin, carbon monoxide, and hydrogen, or a synthetic hydrocarbon obtained by hydrogenating these, and an antioxidant May be added. Alternatively, it is a linear alcohol, acid amide, ester or montan derivative. It is also preferable that impurities such as fatty acids have been removed in advance.

Particularly preferred are those obtained by polymerizing olefins such as ethylene with a Ziegler catalyst, and by-products at this time, such as Fischer-Tropsch wax, whose hydrocarbons have a number of carbon atoms of several thousand, especially about 1,000. Things are good.

From these waxes, the waxes were fractionated according to their molecular weights by using a press sweating method, a solvent method, vacuum distillation, a supercritical gas extraction method, fractional crystallization (for example, melt liquid crystal precipitation and crystal filtration). Wax is used in the present invention.
After fractionation, oxidation, block copolymerization, or graft modification may be performed. For example, those having an arbitrary molecular weight distribution, such as those obtained by removing low molecular weight components by these methods, those obtained by extracting low molecular weight components from these, and those obtained by removing low molecular weight components therefrom.

Waxes fractionated by molecular weight are particularly preferred because they have little effect on triboelectricity and do not adversely affect developability.

The wax used in the present invention has a melting point of 7
0-155 ° C, melt viscosity at 160 ° C is 500c
P or less, melting point of 75 to 145 ° C
The melt viscosity at 140 ° C. is more preferably 1000 cP or less, and the melting point is 80 to 135 ° C .;
It is particularly preferred that the melt viscosity at 0 ° C. is 500 cP or less.

In the toner of the present invention, better results can be obtained when additives are mixed as necessary. As additives, for example, lubricants such as Teflon and zinc stearate, or abrasives such as cerium oxide and silicon carbide,
Alternatively, there are, for example, a fluidity-imparting agent such as aluminum oxide, an anti-caking agent, or a conductivity-imparting agent such as carbon black and tin oxide, or a fixing aid such as low-molecular-weight polyethylene. Further, white fine particles having the opposite polarity can also be used as a developing property improver.

To prepare the positively charged toner according to the present invention, the above-described charge control agent is a vinyl-based or non-vinyl-based thermoplastic resin, a pigment or dye as a colorant, and a magnetic material if necessary. After thoroughly mixing the additives and the like with a ball mill or other mixer, melting, kneading and kneading using a hot kneader such as a heating roll, kneader, extruder, etc. After dispersing or dissolving the content or the dye, solidifying by cooling, pulverizing and classifying, a toner having an average particle diameter of 1 to 20 μm can be obtained.

Alternatively, a method in which the material is dispersed in a binder resin solution and then spray-dried, or a predetermined material is mixed with a monomer to constitute the binder resin to form an emulsified suspension. A polymerization method toner which is polymerized later to obtain a toner,
Alternatively, a method such as a capsule toner comprising a core and a wire can be applied.

[0086]

Examples 1 to 9 and Comparative Examples 1 to 3 100 parts by weight of styrene-butyl acrylate copolymer (copolymerization ratio = 75:25) 80 parts by weight of magnetite 4 parts by weight of low molecular weight ethylene-propylene copolymer 2 parts by weight of charge control agent

[0087]

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After the above materials were mixed well with a blender, they were kneaded with an extruder heated to 130 ° C. After allowing the kneaded material to cool naturally, coarsely pulverize it with a cutter mill, pulverize it using a fine pulverizer using a jet stream, classify it using an air classifier, and charge positively with a weight average particle size of 8.5 μm. Black fine particle size powder with property (hereinafter referred to as black toner)
I got

On the other hand, when the side chain is -C ₃ H ₆ -NH-C ₂ H ₄ -N
H ₂ (nitrogen equivalent: 800, viscosity at 25 ° C .: 8)
0cSt) of the amino-modified silicone oil No. 1 1
Silica (specific surface area: 130 m ² / g) synthesized by a dry method was prepared by diluting 5 parts by weight with n-hexane 4 times.
After spraying, the mixture was heated to 250 ° C. in a nitrogen gas atmosphere and kept for 40 minutes while stirring.

Thereafter, the nitrogen gas was replaced with air, and the mixture was heated at a temperature and time as shown in Tables 1 and 2 with further stirring to carry out an oxidation reaction to obtain an oxidized amino-modified silicone oil silica.

The black toner 100 obtained as described above
0.6 parts by weight of the above treated silica was added to the parts by weight, and mixed with a Henschel mixer to obtain toners according to Examples 1 to 9 and Comparative Examples 1 to 3.

The toner thus obtained is blasted on its surface with spherical beads, and is applied to a commercially available copying machine NP-3020 (manufactured by Canon) having a stainless steel developing sleeve having a plurality of spherical trace depressions. Under a low temperature and low humidity environment (15 ° C./10%) and a normal temperature and low humidity environment (20
(° C./5%), an image output test of 2,000 sheets was performed.
In a high temperature and high humidity environment (32.5 ° C / 90%),
An image output test of 2,000 sheets was performed. Table 1 shows the results.
It is shown in FIG.

Example 10 Instead of the amino-modified silicone oil used in Example 3, amino-modified silicone oil No. having a nitrogen atom equivalent of 400 was used. A toner was obtained and evaluated in the same manner as in Example 3 except that No. 2 was used. Table 3 shows the results.

Example 11 Instead of the amino-modified silicone oil used in Example 3, amino-modified silicone oil No. having a side chain of --C ₃ H ₆ --NH ₂ was used. 3 (nitrogen atom equivalent: 1500, viscosity at 25 ° C .: 80 cSt), except that toner was obtained and evaluated in the same manner. Table 3 shows the results.

[0095] Instead of the amino-modified silicone oil used in Example 12 Example 3, the side chain is _{-C 3 H 6 -N (CH 3} ) - 3 Cl - amino-modified silicone oil is No. 4 (nitrogen equivalent: 10
A toner was obtained and evaluated in the same manner except that the viscosity at 00 and 25 ° C .: 90 cSt) was used. Table 3 shows the results.

Comparative Example 4 Instead of the amino-modified silicone oil of Example 3,
A toner was obtained and evaluated in the same manner except that 3 parts by weight of (C ₂ H ₅ O) ₃ —Si—C ₃ H ₆ —NH ₂ and 17 parts by weight of hexamethyldisilazane were used. Table 3 shows the results.

Example 13 and Comparative Example 5 A toner was obtained in the same manner as in Example 3 except that the following was used instead of the charge control agent, and the same evaluation was performed. Table 3 shows the results.

Embodiment 13

[0099]

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Comparative Example 5 Nigrosine dye

Reference Examples 1-4 and Comparative Reference Example 1 Styrene-butyl acrylate-diethylaminoethyl 75 parts by weight Acrylate copolymer (80: 17: 3) Styrene-butadiene copolymer (80:20) 25 parts by weight Copper phthalocyanine Pigment 5 parts by weight Hydrocarbon wax 4 parts by weight

After thoroughly mixing the above materials with a blender,
The mixture was kneaded with an extruder heated to 130 ° C. After allowing the kneaded material to cool naturally, coarsely pulverize it with a cutter mill, pulverize it using a fine pulverizer using a jet stream, classify it further using an air classifier, and obtain positive chargeability with a weight average particle size of 12 μm. (Hereinafter, referred to as a blue toner) having the following fine particles.

With respect to 100 parts by weight of the blue toner, Table 4
(1) and 0.5 parts by weight of polyvinylidene fluoride particles were added and mixed with a Henschel mixer to obtain respective toners.

Further, a styrene-2-hydroxyethyl methacrylate-methyl methacrylate 50% methyl copolymer (monomer composition weight ratio = 35: 8: 57) a vinylidene fluoride-tetrafluoroethylene copolymer 50% (monomer (Composition weight ratio = 75: 25)

A two-component developer was prepared by mixing 100 parts by weight of a ferrite carrier (average particle size: 65 μm) coated with the above resin and 8 parts by weight of the blue toner. This developer was applied to a color developing device of a copying machine NP-4835 (manufactured by Canon), and 2,000 in a normal temperature and low humidity environment (20 ° C./5%) and a high temperature and high humidity environment (32.5 ° C./90%). One sheet was copied and evaluated.

Table 4 shows the results.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Table 3]

[0110]

[Table 4]

[0111]

According to the present invention, since the above-mentioned heat-treated fine particles are contained, they are not charged excessively even in a low humidity environment. Does not occur, and when a two-component developer is used, there is no occurrence of image density pits, fog, and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-66564 (JP, A) JP-A-63-147170 (JP, A) JP-A-2-273754 (JP, A) JP-A 63-147 73272 (JP, A) JP-A-2-267565 (JP, A) JP-A-59-165068 (JP, A) JP-A-63-225247 (JP, A) JP-A-4-34439 (JP, A) JP-A-2-284153 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08-9/097

Claims (7)

(57) [Claims] 1. A toner containing a binder resin and a triphenylmethane-based compound, wherein the binder resin is a styrene- based compound.
Copolymer is member, and after being treated with a polymer or oligomer having a group containing a nitrogen atom in the side chain, which contains the fine particles subjected to heat treatment at a heating temperature of one hundred eighty to three hundred twenty ° C. in the presence of oxygen A toner characterized by the following. 2. The toner according to claim 1, wherein the toner is a positively chargeable toner. Wherein said polymer or oligomer is attached to the microparticle surface, toner according to claim 1 or 2, characterized in that is present adsorbed or reaction. 4. The fine particles have a specific surface area of 0.1 to 500 m.
The toner according to any one of claims 1 to 3 , wherein the toner is ² / g of inorganic fine particles or resin fine particles. 5. The processing fine particles are used in an amount of 0.01 to toner.
The toner according to any one of claims 1 to 4, wherein the toner is externally added in an amount of from 20 to 20% by weight. 6. The method according to claim 1, wherein the polymer or oligomer is a silicone.
Characterized in that it is a polyene-based polymer or oligomer.
The toner according to any one of claims 1 to 5, wherein 7. The method according to claim 1, wherein the polymer or oligomer is a silicone.
Characterized in that it is silicone varnish or silicone oil
The toner according to any one of claims 1 to 5, wherein