JP3069933B2 - Color toner for electrostatic image development - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner used in a method for developing a latent image.

[0002]

2. Description of the Prior Art Electrophotography is disclosed in U.S. Pat. No. 2,297,6.
As described in, for example, US Pat. No. 91/91, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using toner, and if necessary, the toner image is transferred to a transfer member such as paper, and then fixed by heating, pressure, or solvent vapor to obtain a copy. Further, as a method of developing using a toner or a method of fixing a toner image,
Conventionally, various methods have been proposed, and a method suitable for each image forming process has been adopted.

Conventionally, toners used for these purposes are generally prepared by melt-mixing a coloring agent composed of a dye and a pigment in a thermoplastic resin, uniformly dispersing the same, and then using a pulverizer or a classifier to obtain a toner having a desired particle size. Has been manufactured.

[0004] Although this method can produce fairly good toners, it does have certain limitations, namely the choice of toner materials. For example, the resin colorant dispersion is brittle enough,
It must be able to be comminuted in an economically feasible production equipment. However, when the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at a high speed tends to be widened, and in particular, a relatively large proportion of the fine particles The problem of inclusion occurs. Further, such a highly brittle material is liable to be further pulverized or powdered when used for development in a copying machine or the like. Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin, and depending on the degree of the dispersion, an increase in fog, a decrease in image density, and color mixing / transparency are difficult. Attention must be paid to dispersion, as it will cause defects. Further, exposure of the coloring agent to the fracture surface may cause fluctuations in development characteristics.

On the other hand, in order to overcome the problems of the toner caused by these pulverization methods, Japanese Patent Publication Nos.
Nos. 10799 and 51-14895 propose a method for producing a toner by a suspension polymerization method. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. A continuous phase containing the monomer composition containing a dispersion stabilizer,
For example, the toner particles are dispersed in an aqueous phase using a suitable stirrer, and simultaneously undergo a polymerization reaction to obtain toner particles having a desired particle size.

[0006] Since this method does not include any pulverizing step, the toner does not need to be brittle and a soft material can be used. In addition, the colorant is not exposed to the particle surface, and uniform friction can be obtained. There is an advantage of having a charging property.

However, when a toner is obtained by the conventional suspension polymerization, a spherical toner is obtained, which is suitable for high image quality. However, a spherical toner is obtained by adding various external additives. It is difficult to obtain toner having sufficient properties and sufficient durability. In addition, there are some reports that spherical toner has a strong adhesive force to a photoreceptor and toner cleaning after a transfer process is likely to be insufficient.

In addition, the amount of charge tends to be excessively large in contact charging with a carrier. Particularly, under low temperature and low humidity, the separation of the carrier is significantly reduced, and the developing property is deteriorated. In fact, there are still many points that have not yet been resolved, such as a significant decrease in

Further, the suspension polymerization method toner performs a polymerization reaction of a polymerizable monomer in which a toner property imparting agent such as a colorant and a charge controlling agent is dissolved or dispersed as described above. During the polymerization process, scale adheres to the inner wall surface of the polymerization vessel. In particular, when a large amount of a release agent such as wax is used, a large amount of scale tends to adhere to the inner wall surface of the polymerization vessel. If a large amount of scale adheres to the inner wall surface of the polymerization vessel in this way, it takes a long time to remove and wash the scale, which undesirably lowers productivity and increases costs.

As a means for solving these problems, the anti-blocking property is improved by adding a fluidity-imparting agent such as aluminum oxide to the toner. However, various additives such as the fluidity-imparting agent are usually used. When used for a spherical toner by suspension polymerization, the additive is released from the toner surface or buried inside the toner due to stress such as agitation, causing a problem that the function of the additive is hindered.

Further, since various additives such as these fluidity-imparting agents are added after polymerization, they do not contribute to suppression of scale adhesion.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color toner for developing an electrostatic image, which solves the above-mentioned problems.

An object of the present invention is to provide excellent cleaning properties,
Another object of the present invention is to provide a color toner for developing an electrostatic image having good transferability even under low temperature and low humidity.

An object of the present invention is to provide a color toner for developing an electrostatic charge image, in which scale adherence to the inner wall of a polymerization vessel or the like is small in a polymerization process without changing the toner performance.

[0015]

The object of the present invention is attained by the following constitutions.

That is, the present invention relates to a color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent, and is directly obtained by a suspension polymerization method. Is in the range of the following formula (1), and further contains at least one selected from the group consisting of a zirconium compound, a titanium compound and an yttrium compound in the range of the following formula (2). ) Is a color toner for developing an electrostatic image. 10 ≦ W ≦ 40 (1) 0.001 ≦ A ≦ 1.0 (2) 2 × 10 ⁻⁴ W ≦ A (3) [where W is the amount of the release agent based on 100 parts by weight of the toner binder resin component. A represents parts by weight, and A represents toner binder resin component 1.
It represents parts by weight of zirconium atom, titanium atom or yttrium atom with respect to 00 parts by weight. ]

The present invention also relates to a color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent, and is directly obtained by a suspension polymerization method. Is within the range of the following formula (1) ′, further contains an aluminum compound within the range of the following formula (2) ′, and satisfies the following formula (3) ′ with respect to the release agent. This is a color toner for developing a charge image. 10 ≦ W ≦ 40 (1) ′ 0.01 ≦ A ≦ 1.0 (2) ′ 2 × 10 ⁻³ W ≦ A (3) ′ [where W is the separation from 100 parts by weight of the toner binder resin component. A represents a part by weight of a molding agent, and A represents toner binder resin component 1.
It represents parts by weight of aluminum atoms with respect to 00 parts by weight. ]

Further, the present invention provides a color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent, and is directly obtained by a suspension polymerization method. Is within the range of the following formula (1) ″, further contains an iron compound within the range of the following formula (2) ″, and satisfies the following formula (3) ″ with respect to the release agent. 2 ≦ W ≦ 50 (1) ″ 0.01 ≦ A ≦ 3 (2) ″ 2 × 10 ⁻³ W ≦ A (3) ″ [where W is toner binding] A represents parts by weight of the release agent with respect to 100 parts by weight of the resin component, and A represents the toner binder resin component 1
It represents parts by weight of iron atom with respect to 00 parts by weight. ]

Hereinafter, the present invention will be described in detail.

The present inventors have conducted intensive studies and found that a zirconium compound, a titanium compound, an yttrium compound, an aluminum compound or an iron compound was added to a polymerizable monomer system containing a polymerizable monomer, a colorant, a release agent, and the like. By adding and polymerizing the polymerizable monomer system containing the compound in an aqueous medium by suspension polymerization, a toner having excellent cleaning properties and transferability and having no scale adhesion to the inner wall of the polymerization vessel in the polymerization process can be obtained. I found what I could get.

As a method for incorporating a zirconium compound or the like into the polymerizable monomer system, a method in which zirconium compound powder or the like is added to the polymerizable monomer system is preferable. The zirconium compound used in the present invention is as follows.

The production method and crystal structure of the zirconium compound particles are not particularly limited, but zirconium oxide (zirconia) is preferred.

The properties of the zirconia particles having the same chemical structure vary greatly depending on the manufacturer depending on the firing temperature, time, etc. of the starting material. Particularly, the aggregation form of the zirconia particles and the primary particle diameter are determined by the production method. Differences due to differences are extremely likely to occur.

The zirconia particles used in the present invention are preferably non-agglomerated or easily agglomerated even if they are agglomerated. In the case of zirconia particles containing a so-called "dama" which is strongly agglomerated, It is not preferable because it is difficult to uniformly disperse the toner and lacks in charge stability between toners. In addition, the shape of the particles is extremely angular,
Alternatively, a needle-like shape is not preferable.

The purity of the zirconia particles used in the present invention is not particularly limited as long as they are fine and uniform, and there is no problem as long as they are generally called high-purity zirconia.

The particle size of the zirconium compound used in the present invention is 10 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less.

The other compounds also preferably have the same particle size as the zirconium compound. Titanium oxide (titania) as the titanium compound, yttrium oxide (yttria) as the yttrium compound, aluminum oxide (alumina) as the aluminum compound, iron As long as the compound does not change the color, a compound generally called iron, iron alloy or iron oxide is preferably used. Examples of the iron alloy include, but are not limited to, SUS44 in ASTM and JIS standards.
0C, SUS304, SWRM8, SUJ2, and the like.

As a method for adding a zirconium compound or the like, there is a method using a media type disperser.

Using a bead containing a zirconium compound or the like as a main component as a media, the amount of shaving caused by collision between the media is adjusted by a media-type dispersing machine so that a predetermined amount of zirconium compound powder or the like is mixed into the polymerizable monomer system. The present invention can also be achieved by controlling under the following operating conditions. As the media type dispersing machine, there are FIGS. 1 and 2 and the like.
Attritor [Mitsui Miike Kakoki Co., Ltd.], Sand Grinder [Igarashi Machine Manufacturing Co., Ltd.], Biscomil [Igarashi Machine Manufacturing Co., Ltd.], Pearl Mill [Serizawa Iron Works Co., Ltd.], Dino Mill [Shinmaru Enterprise Co., Ltd.] ], Koball Mill [Shinko Pantech Co., Ltd.], Agitator Mill [K. Bush Shokai], etc., but are not limited thereto. The diameter of the media used is in the range of 0.1 mm to 10 mm, preferably 0.1 mm to 5 mm.
mm. When a media type disperser is used, there is an advantage that the dispersibility of pigments and the like is also improved. It is even better if a predetermined amount of a zirconium compound or the like is mixed and the operating conditions of the media type disperser are controlled so that the dispersibility of the pigment or the like is improved.

In the present invention, when a zirconium compound, a titanium compound or an yttrium compound is used,
The release agent content W is in the range of the following formula (1) with respect to 100 parts by weight of the binder resin component of the toner, and the content A of the zirconium compound or the like satisfies the range of the following formula (2). ,
And it is the range which satisfies the following formula (3) with respect to the release agent content W. Preferably, the release agent content W is in the range of the following formula (4) with respect to 100 parts by weight of the toner binder resin component, and the content A of the zirconium compound or the like satisfies the following formula (5). And the content of the release agent W is within a range satisfying the following expression (3).

10 ≦ W ≦ 40 (1) 0.001 ≦ A ≦ 1.0 (2) 2 × 10 ⁻⁴ W ≦ A (3) 15 ≦ W ≦ 35 (4) 0.001 ≦ A ≦ 1. 0 (5) When the content A of the zirconium compound or the like is more than 1.0 part by weight with respect to 100 parts by weight of the binder resin component of the toner, the charge amount of the toner is reduced, and a developed image is adversely affected. Not preferred. Further, even when the content A of the zirconium compound or the like is more than 0.001 part by weight, if the content A of the release agent is A <2 × 10 ⁻⁴ W, the polymerization reactor in the suspension polymerization process The effect of preventing adhesion of scale to the inner wall or the like cannot be obtained.

Further, when the content W of the release agent is less than 10 parts by weight with respect to 100 parts by weight of the binder resin component of the toner, the fixing point rises and an offset in the fixing is caused, which is not preferable. . On the other hand, if the release agent content W is more than 40 parts by weight based on 100 parts by weight of the binder resin component of the toner, the blocking resistance is lowered and an offset in fixing is undesirably caused.

When an aluminum compound is used in the present invention, the release agent content W is in the range of the following formula (1) ′ with respect to 100 parts by weight of the binder resin component of the toner. The amount A satisfies the range of the following formula (2) ′, and satisfies the following formula (3) ′ with respect to the release agent content W. Preferably, the release agent content W is in the range of the following formula (4) ′ with respect to 100 parts by weight of the toner binder resin component, and the aluminum compound content A is in the range of the following formula (2) ′. And the content of the release agent W satisfies the following formula (3) ′.

10 ≦ W ≦ 40 (1) ′ 0.01 ≦ A ≦ 1.0 (2) ′ 2 × 10 ⁻³ W ≦ A (3) ′ 15 ≦ W ≦ 35 (4) ′ Note that (1) The meanings and reasons for the numerical limitations of () 'to (4)' are the same as in (1) to (5).

Further, when an iron compound is used in the present invention, the content W of the release agent is controlled by the binder resin component 10 of the toner.
The amount of iron compound content A satisfies the range of the following formula (2) ″ with respect to 0 parts by weight, and the iron compound content A satisfies the range of the following formula (2) ″. (3) ". Preferably, the release agent content W is in the range of the following formula (4)" with respect to 100 parts by weight of the toner binder resin component, and further, the iron compound content. A is the following formula (2) "
And the content of the release agent W is satisfied by the following formula (3) ″. More preferably, the content of the release agent W is 100 parts by weight of the toner binder resin component. And the iron compound content A satisfies the following formula (2) ″, and the release agent content W is the following formula (3) ″ Is within the range satisfying.

2 ≦ W ≦ 50 (1) ”0.01 ≦ A ≦ 3 (2)” 2 × 10 ⁻³ W ≦ A (3) ”10 ≦ W ≦ 40 (4)” 15 ≦ W ≦ 35 ( 5) "In addition, the significance and the reason of the numerical limitation of (1)" to (5) "are the same as those of (1) to (5).

The polymerizable monomer constituting the polymerizable monomer system and the toner property imparting agent such as a colorant used in the present invention include the following.

Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate; Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate and the like Acrylic esters, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacryl Phenyl, dimethylaminoethyl methacrylate, methacrylic acid esters other acrylonitrile such as ethyl methacrylate aminoethyl, methacrylonitrile, and the like monomers acrylamide.

These monomers can be used alone or as a mixture. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in a mixture with another monomer, from the viewpoint of the developing characteristics and durability of the toner.

In the present invention, polymerization may be carried out by adding a resin having a polar group to the monomer system. The polar resins that can be used in the present invention are exemplified below. (1) Examples of the cationic polymer include a polymer of a nitrogen-containing monomer such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and a copolymer with styrene, an unsaturated carboxylic acid ester, and the like. (2) Examples of the anionic polymer include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid,
Other examples include unsaturated dibasic acids / unsaturated dibasic acid anhydrides, polymers such as nitro monomers, and copolymers with styrene monomers. These polar resins are localized near the surface of the toner, thereby improving the blocking resistance of the toner.

As the coloring agent used in the present invention, known coloring agents can be used. For example, carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I.
I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I.
Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GT
R, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt,
Brilliant Carmine 3B, Fast Violet B,
Pigments such as methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, final yellow green G and the like. In the present invention, in order to obtain a toner using a polymerization method, it is necessary to pay attention to the polymerization inhibitory and aqueous phase migration properties of the colorant, preferably, surface modification, for example,
It is better to perform a hydrophobic treatment with a substance that does not inhibit polymerization. In particular, attention must be paid to the use of dyes and carbon black since many of them have polymerization inhibitory properties. As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. In addition, regarding carbon black, in addition to the same treatment as the above-described dye, a graft treatment with a substance that reacts with the surface functional group of carbon black, for example, polyorganosiloxane or the like may be performed.

In the present invention, a magnetic substance may be added.
This is also preferably used after performing a surface treatment.

In the present invention, a polyalkylene wax is added as a release agent in an amount of 10 parts by weight or more based on 100 parts by weight of the toner binder resin. It is also possible to use a releasing agent described below in combination for the purpose of improving the toner quality.
For example, in addition to polyolefin-based waxes and modified products thereof, for example, oxides and grafted products, higher fatty acids, metal salts thereof, amide waxes and the like can be mentioned. These waxes have a softening point of 40 to 130 ° C, preferably 50 to 120 ° C according to the ring and ball method (JIS K2531).
C. is desirable. When the softening point is 40 ° C. or less, the blocking resistance and shape retention of the toner are insufficient.
If the temperature is higher than 30 ° C., the effect of the releasability becomes insufficient.

In the present invention, it is desirable to add a charge control agent to the toner material in order to control the chargeability of the toner. As these charge control agents, those having little polymerization inhibition and water phase transfer among known ones are used. For example, as positive charge control agents, nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, amines And polyamine compounds. Examples of the negative charge control agent include metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, styrene-acrylic acid copolymers, and styrene-methacrylic acid copolymers.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1'-azobis (cyclohexane-1-
Azo or diazo polymerization initiators such as carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide are exemplified. These polymerization initiators are preferably added in an amount of 0.5 to 20% by weight of the polymerizable monomer.

In the present invention, a crosslinking agent may be added, and a preferable addition amount is 0.001 to 15% by weight.

The additives used in the present invention for imparting various properties are selected from the viewpoint of durability when added to the toner.
The particle diameter is preferably 1/10 or less of the weight average diameter of the toner particles. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these properties, for example, the following are used.

1) Fluidity imparting agents: metal oxides (such as silicon oxide, aluminum oxide, and titanium oxide), carbon black, and carbon fluoride. Those subjected to a hydrophobic treatment are more preferable.

2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, etc.) , Barium sulfate, calcium carbonate, etc.).

3) Lubricants: fluorinated resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the toner particles.
0.1 to 5 parts by weight are used. These additives may be used alone or in combination of two or more.

The aqueous medium used in the present invention includes:
Eventually a suitable stabilizer is added. For example, as an inorganic compound, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide,
Examples include aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. As an organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and salts thereof, starch and the like can be used by dispersing them in an aqueous phase. This stabilizer is used in an amount of 0.2 parts based on 100 parts of the polymerizable monomer.
It is preferred to use ２０20 parts by weight.

For fine dispersion of these stabilizers, 0.001 to 0.1 parts by weight of a surfactant may be used. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
Examples include sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.

When an inorganic compound is used among these dispersion stabilizers, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be formed in an aqueous medium.

For example, in the case of calcium phosphate, an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride may be mixed under high stirring.

The polymerized toner used in the present invention is obtained by the following method. That is, a mold release agent, a colorant, a charge control agent, a zirconium compound, etc., a polymerization initiator and other additives are added to the polymerizable monomer, and the mixture is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser or the like. The monomer system is dispersed in an aqueous medium containing a dispersion stabilizer using a conventional stirrer or homomixer / homogenizer. Preferably, the granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less. After that, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particle state is maintained and the particles are prevented from settling or floating. After completion of the reaction, while adding an aqueous medium to the suspension, the aqueous medium is distilled off to remove the dispersion stabilizer, and the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, it is generally preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

In the above step, the polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction.

The measurement of the particle size distribution, the melting point of the release agent and the content of zirconium atoms and the like in the present invention will be described.

<Measurement of Particle Size Distribution> A Coulter Counter TA-II type (manufactured by Coulter Inc.) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting a number average distribution and a volume average distribution and a CX-1 personal computer (Canon) And a 1% NaCl aqueous solution is prepared as the electrolytic solution using primary sodium chloride.

The measuring method is as follows.
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5 to 50 mg of a measurement sample is further added.

The electrolyte in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the particle size distribution of particles of 2 to 40 μm was measured using the Coulter Counter TA-II using a 100 μm aperture. Is measured to obtain a volume average distribution and a number average distribution. A weight average particle diameter is obtained from the obtained volume average distribution and number average distribution.

<Melting Point of Release Agent> The temperature of the peak showing the maximum endotherm in the DSC curve at the time of the first temperature rise is performed at a heating rate of 10 ° C./min using DSC-7 (manufactured by PerkinElmer). Was taken as the melting point.

<Measurement of Content of Zirconium Atom, etc.> As a measuring device, a fully automatic fluorescent X-ray analyzer system 308 was used.
0 (manufactured by Rigaku Denki), the relationship between the zirconium oxide content and the diffraction intensity of the Zr element is determined in advance, and then the diffraction intensity of the Zr element of the prepared toner is measured. The content of zirconium oxide in the toner was obtained from the relationship between the diffraction intensities of the elements. From there, the content of Zr atoms was calculated.

For titanium, yttrium, aluminum and iron, titanium oxide, yttrium oxide, aluminum oxide and iron powder were used, respectively, and the content of Ti, Y, Al and Fe atoms was determined in the same manner as described above. Was calculated.

Hereinafter, the present invention will be specifically described based on examples.

[0067]

Example 1 451 g of a 0.1 M Na ₃ PO ₄ aqueous solution was added to 709 g of ion-exchanged water and heated to 60 ° C., and then, using a TK homomixer (manufactured by Tokushu Kika Kogyo) at 12,000 rpm. And stirred. A 1.0 M CaCl ₂ aqueous solution was added to the mixture.
7 g was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene 170 g 2-ethylhexyl acrylate 30 g C.I. I. Pigment Blue 15: 3 10 g Paraffin wax (mp 70 ° C.) 60 g Metal compound di-tert-butylsalicylate 5 g Zirconium oxide 0.4 g The above formulation was heated to 60 ° C. Was uniformly dissolved and dispersed at 12,000 rpm. Into this, a polymerization initiator, 10 g of 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of dimethyl 2,2′-azobisisobutyrate were dissolved to prepare a polymerizable monomer system. The above-mentioned polymerizable monomer system is charged into the above-mentioned aqueous medium, and the mixture is heated at 10,000 rpm and TK homomixer at 60 ° C. in an N ₂ atmosphere.
After stirring for minutes, the polymerizable monomer system was granulated. Then, after reacting at 60 ° C. for 3 hours while stirring with a paddle stirring blade,
The liquid temperature was set to 80 ° C., and the reaction was performed for 10 hours.

Thereafter, the mixture was cooled, hydrochloric acid was added, and Ca ₃ (P
O ₄ ) ₂ was dissolved, filtered, washed with water and dried to obtain a polymerized toner. The particle diameter of the obtained toner is 8.5 μm in weight average diameter.
m and had a sharp particle size distribution. After completion of the polymerization, the degree of adhesion of the scale on the inner wall of the polymerization vessel was visually examined. Table 1 shows the results.

With respect to 100 parts by weight of the obtained toner, B
0.7 parts by weight of a hydrophobic silica having a specific surface area of 200 m ² / g by the ET method was externally added. 93 parts by weight of an acryl-coated ferrite carrier was mixed with 7 parts by weight of this toner to prepare a developer.

Using this developer and an externally added toner, an image was formed at a low temperature and a low humidity with a full color copying machine CLC-500 manufactured by Canon Inc., and an offset evaluation at the time of fixing was performed. Table 1 shows the results.

Example 2 In Example 1, the amount of zirconium oxide was changed to the resin component 10
Polymerized toner was obtained by performing the same operation except that the amount was 0.003 parts by weight with respect to 0 parts by weight and the amount of paraffin wax was 15 parts by weight with respect to 100 parts by weight of the resin component. The obtained toner had a weight average particle size of 8.7 μm and a sharp particle size distribution.

After the completion of the polymerization, the degree of adhesion of the scale on the inner wall surface of the polymerization vessel was visually inspected in the same manner as in Example 1, and a developer was prepared. Was evaluated for offset. Table 1 shows the results.

Example 3 In Example 1, the amount of zirconium oxide was changed to the resin component 10
Polymerized toner was obtained by performing the same operation except that the amount was 0.007 parts by weight with respect to 0 parts by weight and the amount of paraffin wax was 35 parts by weight with respect to 100 parts by weight of the resin component. The obtained toner had a sharp particle size distribution with a weight average particle size of 8.4 μm.

After completion of the polymerization, the degree of scale adhesion on the inner wall surface of the polymerization vessel was visually inspected in the same manner as in Example 1, and a developer was prepared. The offset was evaluated. Table 1 shows the results.

Example 4 Formulation I Styrene 1500 g C.I. I. Pigment Blue 15: 3 150 g Metallic compound of di-tert-butylsalicylate 30 g 5 mm containing zirconium oxide as a main component as a mediator
The formulation I was dispersed at 200 rpm for 3 hours using φ beads and an attritor MA-1S (manufactured by Mitsui Miike Kakoki Co., Ltd.) as a media type disperser.

Formulation II Formulation I (attritor-treated product) 112 g Styrene 70 g 2-Ethylhexyl acrylate 30 g Paraffin wax (mp 70 ° C.) 60 g The same operation as in Example 1 was carried out on Formula II to obtain a polymerized toner. Was. The obtained toner particle diameter was 8.5.
It had a sharp particle size distribution at μm. When the content of zirconium atoms was measured by the fluorescent X-ray measurement, the content was 0.3 parts by weight with respect to 100 parts by weight of the resin component of the toner, and the zirconia compound was added as initially set. It was confirmed that.

After completion of the polymerization, the degree of adhesion of the scale to the inner wall surface of the polymerization vessel was visually examined in the same manner as in Example 1, and a developer was prepared. The offset was evaluated. The result was equivalent to that of Example 1. Table 1 shows the results.

Example 5 Formulation I Styrene 1500 g C.I. I. Pigment Blue 15: 3 150 g Di-tert-butylsalicylic acid metal compound 30 g 2 mm mainly composed of zirconium oxide as a media
Using φ beads and using an attritor MA-1S (manufactured by Mitsui Miike Kakoki Co., Ltd.) as a media type disperser, the above-mentioned formulation I was dispersed at a rotation speed of 300 rpm for 3 hours.

Formulation II Formulation I (attritor-treated product) 112 g Styrene 70 g 2-Ethylhexyl acrylate 30 g Paraffin wax (mp 70 ° C.) 60 g The same operation as in Example 1 was carried out on Formula II to obtain a polymerized toner. Was. The obtained toner particle diameter was 8.5.
It had a sharp particle size distribution at μm. Further, when the content of zirconium atoms was measured by the above-mentioned fluorescent X-ray measurement, it was found that the content of zirconium atom was 0.22 parts by weight based on 100 parts by weight of the resin component of the toner.
Parts by weight, and it was confirmed that the zirconium compound was added as originally set.

After completion of the polymerization, the degree of adhesion of the scale to the inner wall surface of the polymerization vessel was visually inspected in the same manner as in Example 1, and a developer was prepared. The offset was evaluated. The result was equivalent to that of Example 1. Table 1 shows the results.

Comparative Example 1 A polymerized toner was obtained in the same manner as in Example 1 except that zirconium oxide was not added.
The obtained toner had a weight average particle size of 8.7 μm and a sharp particle size distribution.

After completion of the polymerization, the degree of adhesion of the scale on the inner wall surface of the polymerization vessel was visually inspected in the same manner as in Example 1, and a developer was prepared. Was evaluated for offset. Table 1 shows the results.

Comparative Example 2 In Example 1, the amount of zirconium oxide was changed
The same operation was performed except that the amount was changed to 2.5 parts by weight with respect to 0 parts by weight to obtain a polymerized toner. The obtained toner had a weight average particle size of 8.8 μm and a sharp particle size distribution. After completion of the polymerization, the degree of scale adhesion on the inner wall surface of the polymerization vessel is visually inspected in the same manner as in Example 1, a developer is prepared, an image is formed under a low temperature and a low humidity, and an offset at the time of fixing is evaluated. Was performed. Table 1 shows the results.

Comparative Example 3 In Example 1, the amount of paraffin wax was
A polymerized toner was obtained by performing the same operation except that the amount was 1 part by weight with respect to 00 parts by weight. The particle size of the obtained toner is
It had a sharp particle size distribution with a weight average diameter of 8.6 μm. After completion of the polymerization, the degree of scale adhesion on the inner wall surface of the polymerization vessel is visually inspected in the same manner as in Example 1, a developer is prepared, an image is formed under a low temperature and a low humidity, and an offset at the time of fixing is evaluated. Was performed. Table 1 shows the results.

Comparative Example 4 In Example 1, the amount of paraffin wax was
A polymerized toner was obtained by performing the same operation except that the amount was 55 parts by weight with respect to 00 parts by weight. The obtained toner had a sharp particle size distribution with a weight average particle size of 8.5 μm. In the same manner as in Example 1, the degree of adhesion of the scale to the inner wall surface of the polymerization vessel was visually inspected, a developer was prepared, an image was formed under low temperature and low humidity, and the offset at the time of fixing was evaluated. Table 1 shows the results.

[0087]

[Table 1] 1) Scale adhesion: ◎ hardly adhered, ○ slightly adhered, Δ slightly adhered, × adhered 2) Image density under low temperature and low humidity: ◎ good, ○ relatively good, △
Slightly inferior, × inferior 3) Offset property during fixing: good, good, Δ slightly inferior, × inferior Examples 6 to 10 and comparative examples 5 to 7 zirconium oxide in Examples 1 to 5 was replaced with titanium oxide Each of the examples was repeated in exactly the same manner, except that a titanium oxide-containing developer (Examples 6 to 10) was prepared and evaluated. Table 2 shows the results.

Table 2 also shows a case where each comparative example was repeated (Comparative Examples 5 to 7) in exactly the same manner except that zirconium oxide in Comparative Examples 2 to 4 was replaced with titanium oxide.

[0089]

[Table 2] 1) The content of titanium atoms by X-ray fluorescence measurement was 0.24 parts by weight with respect to 100 parts by weight of the toner resin component, and the titanium compound was added as initially set. 2) The content of titanium atoms by X-ray fluorescence measurement was 0.18 parts by weight with respect to 100 parts by weight of the toner resin component, and the titanium compound was added as initially set.

Examples 11 to 15 and Comparative Examples 8 to 10 The same procedures as in Examples 1 to 5 were repeated except that zirconium oxide was replaced with yttrium oxide. Examples 11 to 15) were prepared and evaluated. Table 3 shows the results.

Table 3 also shows a case where each comparative example was repeated (Comparative Examples 8 to 10) in exactly the same manner except that zirconium oxide in Comparative Examples 2 to 4 was replaced with yttrium oxide.

[0092]

[Table 3] 1) The content of the yttrium atom by the fluorescent X-ray measurement is
The amount was 0.16 parts by weight based on 100 parts by weight of the toner resin component, and the yttrium compound was added as originally set. 2) The content of the yttrium atom by the fluorescent X-ray measurement is
The amount was 0.12 parts by weight based on 100 parts by weight of the toner resin component, and the yttrium compound was added as originally set.

Examples 16 to 20 and Comparative Examples 11 to 13 A developer (Example 16) was prepared in the same manner as in Example 1 except that 0.4 g of zirconium oxide in Example 1 was replaced by 1 g of aluminum oxide. did.

Further, the zirconium oxide in Example 2 was added in an amount of 0.1%.
A developer in which 002 parts by weight was replaced with 0.03 parts by weight of aluminum oxide (Example 17), and a developer in which 0.007 parts by weight of zirconium oxide in Example 3 was replaced with 0.07 parts by weight of aluminum oxide (Example 17) Example 18) was prepared.

Further, developers (Examples 19 and 20) were prepared in exactly the same manner as in Examples 4 and 5, except that zirconium oxide was replaced with aluminum oxide.

Table 4 shows the results.

A developer (Comparative Example 11) was prepared in the same manner as in Comparative Example 2, except that zirconium oxide in Comparative Example 2 was replaced with aluminum oxide. Table 4 shows the results.

Each of the comparative examples was repeated in the same manner as in Comparative Examples 3 and 4, except that 0.2 part by weight of zirconium oxide was replaced by 0.5 part by weight of aluminum oxide (Comparative Examples 12 and 13). Is also shown in Table 4.

[0099]

[Table 4] 1) The content of aluminum atoms by fluorescent X-ray measurement is
The amount was 0.27 parts by weight based on 100 parts by weight of the toner resin component, and the aluminum compound was added as originally set. 2) The content of aluminum atoms by fluorescent X-ray measurement is
The amount was 0.21 part by weight based on 100 parts by weight of the toner resin component, and the aluminum compound was added as originally set.

Examples 21 to 25 and Comparative Examples 14 to 17 A developer (Example 21) was prepared in the same manner as in Example 1 except that 0.4 g of zirconium oxide in Example 1 was replaced by 1 g of iron powder.
Was prepared.

Further, the zirconium oxide 0.1 in Example 2 was used.
The developer in which 002 parts by weight was replaced with 0.03 parts by weight of iron powder (Example 22), the zirconium oxide 0.0 in Example 3 was used.
A developer was prepared in which 07 parts by weight was replaced with 0.07 parts by weight of iron powder (Example 23).

Further, except that the zirconium oxide in Examples 4 and 5 was changed to iron powder, and the dispersion time of Formulation I using the media type disperser in Examples 4 and 5 was changed to 1 hour. The developer (Example 24) was carried out in exactly the same manner as in Examples 4 and 5.
And 25) were prepared.

Table 5 shows the results.

The zirconium oxide 25 in Comparative Example 2
A developer (Comparative Example 14) was prepared in the same manner as in Comparative Example 2, except that 5.5 parts by weight of iron powder was used instead.

Further, zirconium oxide in Comparative Example 3 was added in an amount of 0.1%.
A developer (Comparative Example 15) was prepared in the same manner as in Comparative Example 3, except that 2 parts by weight was replaced with 0.5 part by weight of iron powder (based on 100 parts by weight of the resin component).

The zirconium oxide 0.1 in Comparative Example 4 was used.
A developer (Comparative Example 16) was prepared in the same manner as in Comparative Example 4, except that 0.5 parts by weight of iron powder was used instead of 2 parts by weight.

Further, zirconium oxide in Comparative Example 2 was used.
Comparative Example 2 except that 5 parts by weight was changed to 0.02 parts by weight of iron powder and the particle size of the obtained toner was changed to a weight average diameter of 8.6 μm.
A developer (Comparative Example 17) was prepared in the same manner as described above.

Table 5 shows the results.

[0109]

[Table 5] 1) The content of iron atoms in the fluorescent X-ray measurement was 0.61 part by weight with respect to 100 parts by weight of the toner resin component, and the iron compound was added as initially set. 2) The content of iron atoms measured by X-ray fluorescence was 0.42 parts by weight based on 100 parts by weight of the toner resin component, and the iron compound was added as initially set.

[0110]

The toner according to the present invention has a sharp particle size distribution, has excellent cleaning properties under low temperature and low humidity, and has good transferability, so that a good image having environmental stability without lowering the image quality can be obtained. Can be provided. Furthermore, the scale adheres little to the inner wall of the polymerization vessel during the polymerization process, so that the productivity is high.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a media type disperser.

FIG. 2 is a schematic view showing another example of a media type disperser.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kasugani Rare 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (56) References JP-A-56-123553 (JP, A) JP-A-62-70863 (JP, A) JP-A-63-118757 (JP, A) JP-A-2-251860 (JP, A A) JP-A-3-114059 (JP, A) JP-A-4-347864 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (12)

(57) [Claims] 1. A color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent and is directly obtained by a suspension polymerization method, the content of the release agent is represented by the following formula ( (1) and further contains at least one selected from a zirconium compound, a titanium compound and an yttrium compound in the range of the following formula (2), and satisfies the following formula (3) with respect to the release agent. A color toner for developing electrostatic images, characterized by the following. 10 ≦ W ≦ 40 (1) 0.001 ≦ A ≦ 1.0 (2) 2 × 10 ⁻⁴ W ≦ A (3) [where W is the amount of the release agent based on 100 parts by weight of the toner binder resin component. A represents parts by weight, and A represents toner binder resin component 1.
It represents parts by weight of zirconium atom, titanium atom or yttrium atom with respect to 00 parts by weight. ] 2. The electrostatic image according to claim 1, wherein the release agent is a polyalkylene wax and is contained in an amount of 10 parts by weight or more based on 100 parts by weight of the toner binder resin component. Color toner for development. 3. The method according to claim 2, wherein the zirconium compound is zirconium oxide.
3. The static electricity according to claim 1, wherein
Color toner for developing charge images. 4. The method according to claim 1, wherein the titanium compound is titanium oxide.
The electrostatic charge according to claim 1 or 2, wherein
Color toner for image development. 5. The method according to claim 1, wherein the yttrium compound is an yttrium oxide.
3. The static electricity according to claim 1, wherein
Color toner for developing charge images. 6. A color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent, and is directly obtained by a suspension polymerization method, the content of the release agent is represented by the following formula: 1) ′, further comprising an aluminum compound in the range of the following formula (2) ′, and satisfying the following formula (3) ′ with respect to the release agent: Color toner. 10 ≦ W ≦ 40 (1) ′ 0.01 ≦ A ≦ 1.0 (2) ′ 2 × 10 ⁻³ W ≦ A (3) ′ [where W is the separation from 100 parts by weight of the toner binder resin component. A represents a part by weight of a molding agent, and A represents toner binder resin component 1.
It represents parts by weight of aluminum atoms with respect to 00 parts by weight. ] 7. The electrostatic image according to claim 6 , wherein the release agent is a polyalkylene wax and is contained in an amount of 10 parts by weight or more based on 100 parts by weight of the toner binder resin component. Color toner for development. 8. The method according to claim 1, wherein the aluminum compound is aluminum oxide.
The static electricity according to claim 6 or 7, wherein
Color toner for developing charge images. 9. In a color toner for developing an electrostatic image, which contains at least a binder resin, a colorant and a release agent and is directly obtained by a suspension polymerization method, the content of the release agent is represented by the following formula: 1) ", further comprising an iron compound in the range of the following formula (2)", and satisfying the following formula (3) "with respect to the release agent: 2 ≦ W ≦ 50 (1) ″ 0.01 ≦ A ≦ 3 (2) ″ 2 × 10 ⁻³ W ≦ A (3) ″ [where W is based on 100 parts by weight of the toner binder resin component] A represents a part by weight of the release agent, and A represents toner binder resin component 1.
It represents parts by weight of iron atom with respect to 00 parts by weight. ] 10. The content of the release agent is represented by the following formula (4) ″:
And an iron compound in the range of the following formula (2) ″
And satisfy the following formula (3) ″ for the release agent
The color for developing an electrostatic image according to claim 9,
-Toner. 10 ≦ W ≦ 40 (4) " 0.01 ≦ A ≦ 3 (2) " 2 × 10 ^-3 W ≦ A (3) " 11. The release agent is the polyalkylene waxes and also claim 9, characterized in that it contains more than 10 parts by weight based on the toner binder resin 100 parts by weight of component
11. The color toner for developing an electrostatic image according to item 10 . 12. The iron compound is iron, an iron alloy or iron oxide.
Characteristic of being a thing Any one of claims 9 to 11
3. The color toner for developing an electrostatic image according to item 1.